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Lithium ion secondary battery
Lithium ion secondary battery(Lithium-ion battery,British: lithium-ion battery) IsPositive electrodeとNegative electrodeBetweenlithiumionBy movingCharging,DischargeI doSecondary batteryIs. Positive electrode, negative electrode,ElectrolyteEach material varies depending on the application and manufacturer, but a typical configuration is for the positive electrode.Lithium transition metal composite oxide, To the negative electrodecarbonFor materials and electrolytesOrganic solventNon-aqueous electrolyte such as. simplyLithium ion battery,lithium ionbattery,Li-ion battery,LIB,LiBAlso say. The name lithium-ion secondary batterySony Energy TechBy Keizaburo Tozawa.
The batteries with similar names are as follows.
- Lithium batteryUse for the negative electrodePrimary battery.. Lithium ionElectrical conductionIt is the same as a lithium-ion battery in that it plays a major role, but one that uses metallic lithium for the negative electrode is usually distinguished from a lithium-ion battery. The reason for this is that the reaction on the negative electrode side is the dissolution/precipitation reaction of the lithium metal itself, and lithium ions enter and leave between the graphite layered structures as in the case of using graphite.IntercalationThis is because it is different from the lithium ion battery according to. Application to secondary batteries has been tried many times, but the structure of the battery is destroyed and deteriorates due to the deposition of metal needle crystals during charging.DendriteThe problem as a dangerous substance due to the reactivity of metallic lithium cannot be overcome and is not widely used.
- Lithium polymer battery(LiPo battery) is a type of lithium-ion battery that can be used as an electrolyte.gelStatepolymer(High molecular) Rechargeable battery.
- Lithium iron phosphate battery(LiFe battery) is a type of lithium-ion battery and is a secondary battery that uses the positive electrode material.
Identification color■Blue (cyan).
1980s,Mobile phone,laptopDue to the development of portable devices such asSecondary batteryAlthough the need for (rechargeable batteries) has increased,Nickel hydride batteryThere was a limit to the capacity-to-weight ratio, and there was a longing for a new secondary battery.[Source required].
1976 years,Exon OfStanley WhittinghamDeveloped and proposed a secondary battery that uses titanium disulfide for the positive electrode and metallic lithium for the negative electrode... This battery has not been put to practical use because there are safety problems (dendrite problem at the time of charging, metallic lithium reactivity problem) especially on the negative electrode side, but titanium disulfide is a layered compound, and lithium ion is a molecule. It was a substance that had a space that could be stored at a level, and had the characteristic that its shape would not easily break even if lithium ions repeatedly entered and left. The phenomenon that "ions enter and leave the layered compound" isIntercalationIt is called "." Due to its excellent characteristics, intercalation type electrodes have been actively studied thereafter.
1974-1976,Technical University of Munich OfBesenhardt ThegraphiteReversible intercalation of lithium ions withinAnd of the cathodeOxideFound intercalation to.. In 1976, Besenhardt proposed application in lithium batteries.. (However, graphite isAlkali metalTake in etcIt has been known since 1926. )
However, when graphite is used for the negative electrode, it is a common electrolyte at the time.Propylene carbonateMost of them (used in lithium metal batteries)organic matterWill decompose on the negative electrode sideTherefore, it has been considered difficult to stably and electrochemically intercalate lithium ions in a carbon-based material using an organic electrolytic solution. In other words, it has been difficult to put a secondary battery using graphite into the negative electrode into practical use.
1980 years,Oxford University OfJohn GoodenoughとKoichi MizushimaAre compounds of lithium and cobalt oxideLithium cobalt oxide (LiCoO2) LithiumTransition metalOxideWas proposed as the positive electrode material.. This is the origin of the positive electrode of the lithium ion secondary battery.
On the other hand, at the time of Kyoto UniversityTokio YamabePolyacene-based polymeric carbon material proposed based on their quantum chemical designHowever, it attracted attention in the name of one-dimensional graphite, and its creation was tried in various places. In response to this, in 1981,KaneboIs a kind of stable non-graphitizable carbonOrganic semiconductorCreate (PAS), Two kinds of batteries were developed using this, and both were put into practical use. One is a capacitor-type battery (PAS battery) that uses PAS for both, and the other uses a PAS in which the negative electrode is pre-doped with Li ions (Lithium ion capacitor). In the latter, the positive electrode operates similarly to a capacitor, and the negative electrode operates similar to a lithium ion battery. Thus, it was discovered for the first time that PAS enables smooth and stable Li-doping and de-doping even with carbon materials. The development of carbon materials for electrodes including easy graphitization was decided by everyone..
1983 years,And John Goodenough and othersSpinel structureHave (LiMn2O4) Was introduced as a positive electrode material.. Compared with lithium cobalt oxide, it is cheap and safe. (It was put into practical use as a positive electrode material in 1996, and is commonly used as well as lithium cobalt oxide.)
1986, CanadianTo the positive electrodeMolybdenum sulfide, A metallic lithium secondary battery using metallic lithium for the negative electrode was commercialized, but because the chemical activity of metallic lithium is extremely high, it is reversible.DendriteIs deposited and grown, and it contacts the positive electrodeShort circuitAnd the reactivity (even a small amount of contact with water causes intense fever).hydrogenThere is a problem in (danger of generating gas and igniting). In 1989, a series of fire accidents occurred at NTT shoulder type mobile phones, etc.It was hard to say that it was put to practical use, and metallic lithium was used for the negative electrode.Primary batteryIs commercially available, but its application to secondary batteries is dangerous and has not been widely used.
In 1990, when graphite was used for the negative electrode,Ethylene carbonateIt was discovered that the decomposition reaction of the organic electrolyte can be stopped by forming a protective film on the surface of graphite, though it decomposes in the initial charging.. (In 1994Matsushita Battery IndustryHas been adopted as an electrolytic solution bysolventIs used as. )
Creation and realization of lithium-ion secondary batteries
Asahi Kasei OfYoshino Akira(2019 Nobel Prize in Chemistry) et al.Hideki ShirakawaConducting electricity discovered in 2000 by the 1977 Nobel Prize in ChemistryPlasticIsPolyacetylenePaying attention to, in 1981Organic solventIt was found that it is suitable for the negative electrode of the secondary battery using. For the positive electrode, John Goodenough and others discovered it in 1980.Lithium cobalt oxide (LiCoO2) And other lithium transition metal oxides were used to create prototypes of lithium-ion secondary batteries in 1983... However, polyacetylene has problems that it has a low true specific gravity and does not increase the battery capacity, and that it is unstable as an electrode material. So in 1985, Yoshino and his colleaguescarbonThis is a new secondary battery that uses the material as the negative electrode and lithium cobalt oxide containing lithium as the positive electrode.Lithium-ion secondary battery (LIB)Established the basic concept of.
LIB was born when Akira Yoshino focused on the following points.
- Positive electrodeIf lithium cobalt oxide is used for
- Since the positive electrode itself contains lithium, it is not necessary to use metallic lithium for the negative electrode, so it is safe.
- 4 VHigh classpotentialHave a high capacity
- Negative electrodeIf a carbon material is used for
- Since the carbon material occludes lithium, metallic lithium is essentially absent from the battery, so it is safe.
- Large capacity of lithium storage
in addition,Aluminum foilTechnology for using a positive electrode current collector, A functional separator to ensure safetyEstablished technologies for essential battery constituent elements such asWe have developed technologies such as protection circuit/charge/discharge technology, electrode structure/battery structure, etc.VoltageSucceeded in commercializing a battery similar to a metallic lithium secondary battery, and almost completed the current LIB configuration.
Commercialization and subsequent trends
1991 years,Sony Energy TechWas the first in the world to commercialize a lithium-ion battery. Then in 1993, AT Battery (Asahi KaseiとToshibaCommercialized by a joint venture withSanyo ElectricHas commercialized a lithium-ion battery using graphite carbon as a negative electrode material.
1997, and John Goodenough and othersOlivine structureHave (lifepo4) Was proposed as the positive electrode material.. Compared with lithium cobalt oxide, it is safe and has a long life. In 2009, SonyLithium iron phosphate batteryWas commercialized. It is currently sold by each company.
1999 with Sony Energy TechMatsushita Battery IndustryIs the electrolytegelStatepolymeruseLithium ion polymer batteryWas commercialized. By changing the electrolyte from a liquid to a quasi-solid polymer, it is possible to make it thinner and lighter.Short circuitThe resistance to overcharging has also improved. The exterior is also conventional鉄,aluminumNot a can ofRetort foodIt is now possible to use simple things such as used for. Rapidly popularized in the 2000s mainly for mobile electronic devices, nowadaysSmartphone,Mobile phoneThe batteries used in the are almost all lithium-ion polymer batteries. In the 2010sWearable equipment,DroneThe use is spreading to emerging industries such as.
In 2008, Toshiba turned negativeLithium titanate (Li4Ti5O12) Has been commercialized. Compared to carbon materials, it has features such as safety, long life, rapid charging, and low temperature operation, but the potential is about 1.5V higher than graphite, so the voltage of a single cell becomes lower and the energy density is slightly lower. is there. Currently for automobiles (installation example:Suzuki Wagon R), industrial use, electric power storage, etc.
Lithium-ion batteries are becoming increasingly popular for automobiles, and since around 2009 they have been in full swing.Hybrid carStarted to be used. Since then, the number of adopted cars has increased,Honda fit hybrid,Toyota PriusIt has also been adopted for popular car models such as. Automotive lithium-ion batteries are a joint venture between an automobile manufacturer and a battery manufacturer (Prime Earth EV Energy,Lithium Energy Japan,Blue energy) BesidesPanasonic,ToshibaElectrical machinery manufacturers,Hitachi Vehicle EnergyEtc. AlsoToyota,Nissan,HondaAlthough automobile manufacturers are also conducting research and development, solid materials are used as electrolytes at the development stage, but they are drawing attention as next-generation secondary batteries. Hybrid cars andElectric carThe market size of lithium-ion batteries for automobiles is still expanding as 2015 due to the popularization of
Lithium-ion batteries used to have a high share of Japanese manufacturers, and there was a time when they accounted for more than 9%. Sanyo, Sony,Panasonic Energy Company,Hitachi Maxell,NEC TOKINAre known as the main manufacturers. on the other hand, South Korea(Samsung SDI,LG Chem),Chugoku (BYD,CATL),TaiwanProduction is increasing.
Contribution/impact to society
Currently, lithium-ion secondary batteries (LIB)Mobile phone,laptop,Digital camera-videoInstalled in a wide range of electronic and electric devices including portable music players, the LIB market grew to 2010 trillion yen in 1.. The convenience of portable IT devices is greatly increased by installing a small and lightweight LIB. Make a contribution. Also, LIB isEco carと 呼 ば れ るAutomobile (EV, HEV, P-HEV)TrainIt is being put to practical use as a power source for transportation such assmart gridPower storage devices are also being actively researched. Other than that,rocket,Artificial satelliteAsteroid probeHayabusa-Hayabusa 2,Stork(HTV),International Space Station(ISS)Such asSpace developmentField,Soryu SubmarineOf the 11th shipOryu,Taigei-class submarineIt is also installed in ships such as.
1997 years,Tokio YamabeHas been awarded the Japan Chemistry Award for the achievement of the world's first basic research on the development of a lithium-ion secondary battery using a non-graphitizable carbon material as the negative electrode.
The achievement of inventing the lithium-ion secondary battery was evaluated, and in 2014, John Goodenough,Nishi Mio,, Yoshino Akira are called "Nobel Prize in Engineering"Charles Stark Draper AwardAwardIn 2019, three members, John Goodenough, Stanley Whittingham, and Akira YoshinoNobel Prize in ChemistryWon.
There are various types of lithium-ion batteries,Positive electrode,Negative electrode,ElectrolytePerformance changes depending on the combination of materials. The following is a rough classification of popular items... It should be noted that the performance and safety are improved even by devising additives and coating electrodes, so that it is actually more complicated.
|Positive electrode||Negative electrode||Voltage||Energy density|
① Wh / kg
② Wh / L
① Charging speed
② Discharge rate
|Operating temperature limit|
① When charging
② During discharge
|Cycle life||安全 性|
① Thermal runaway temperature in heating
② Thermal runaway temperature due to overcharge
③ Thermal runaway with nail penetration
④ Gas generation by nail piercing
|Lithium cobalt oxide|
|graphite||3.6 3.7-V||① 150-240||① 0.7-1 C|
② 1 C
|① 0 ℃ ~ 45 ℃|
② -20℃ to 60℃
|500-1000||① 188 ℃ → 527 ℃ (smoke, ignition)|
② 110 ℃ → 317 ℃ (smoke, fire)
4 H2,CO,CO2,HF(Very small amount)
And many others
|Commercialized in 1991, it is widely used mainly for mobile devices.cobaltHowever, the problem is that they are expensive and have large price fluctuations.Thermal runawayBecause of the risk, it is rarely used for automobiles.|
|graphite||3.7 3.8-V||① 100-150||① 0.7-3 C|
② 1-10 C
|② -20℃ to 50℃||300-700||① 283℃→474℃ (smoke)|
② 103 ℃ → 555 ℃ (smoke)
Lithium Energy Japan
Hitachi Vehicle Energy
|Commercialized in 1996, it has become widespread especially for automobiles in recent years.Crystal structureHas relatively high heat stability. Of materialmanganeseIs less than 1/10 the price of cobalt. Cycle life and elution of manganese at high temperature were issues, but they have been improved in recent years.|
|graphite||3.2 3.3-V||① 90-120||① 1 C|
② 1-25 C
|② -20℃ to 60℃||1000-2000||① 186℃→267℃ (smoke)|
② 109 ℃ → 179 ℃ (smoke)
4 HF(Very small amount)
Power storage system
|In recent years, adoption has been increasing in the United States and China. The material is cheap, but the manufacturing cost is rather high. High thermal stability due to its strong crystal structure. The problem was that the electrical conductivity was low, but it has been improved by making the active material finer and adopting a carbon coating on the surface.|
|Three-way system (NMC system)|
|graphite||3.6 3.7-V||① 150-220||① 0.7-1 C|
② 1-2 C
|② -20℃ to 60℃||1000-2000||① 242 ℃ → 429 ℃ (smoke, ignition)|
② 105 ℃ → 606 ℃ (smoke, fire)
4 H2,CO,CO2,HF(Very small amount)
Lithium Energy Japan
|The ternary system isnickel,manganese,cobaltThe threeelementIt was developed in Japan and the United States in 2000.|
|Nickel system (NCA system)|
|graphite||3.6 V||① 200-260||① 0.7 C|
② 1 C
|② -20℃ to 60℃||500||Medical equipment|
|Prime Earth EV Energy|
|originally(LiNiO2) Was known to have a higher energy density than lithium cobalt oxide, but it was difficult to put it to practical use due to safety issues. In NCA system,nickelFor structural stabilization on the basecobaltTo improve heat resistancealuminumIs also added to the negative electrodeceramicBy coating the layers, heat resistance is increased and safety is improved.|
|2.4 V||① 70-80||① 1-5 C|
② 10-30 C
|② -30℃ to 60℃||3000-7000||① No thermal runaway up to 300℃|
Power storage system
|It was commercialized by Toshiba in 2008. Toshiba's SCiB does not easily cause thermal runaway even if an internal short circuit occurs due to external force, long life of 10000 times or more of charge and discharge, quick charge in 6 minutes,CapacitorIt is said that it has similar input/output density and can be used in cold regions (-30°C).|
In a typical configuration,Negative electrodeTocarbon,Positive electrodeToLithium cobalt oxideLithium transition metal oxides, such asElectrolyteToEthylene carbonate,Diethyl carbonateSuch asOrganic solvent + Lithium hexafluorophosphate (LiPF6) Such as lithium salt is used. However, in general, each of the materials for the negative electrode, the positive electrode, and the electrolyte need only move lithium ions and can be charged and discharged by giving and receiving charges, and thus can have a great many configurations.
For lithium salt LiPF6 In addition,LiBF4 Fluorine-based complex salts such asLiN (SO)2Rf)2・ LiC (SO)2Rf)3 (However, Rf = CF3,C2F5), etc. are also used.
Also, in order to give high conductivity and safety to the electrolyte,Ethylene carbonate-Propylene carbonateSuch as ringCarbonate esterIt is a low-viscosity solvent as well as a high-dielectric constant/high-boiling point solvent.Dimethyl carbonate,Diethyl carbonateIn some cases, a lower chain carbonic acid ester such as is used and a lower chain is partially used.
The electrochemical reaction in a lithium ion battery is composed of a positive electrode, a negative electrode and an electrolyte. In both the positive electrode and the negative electrode, lithium ions can penetrate into the material. That lithium moves inside the positive and negative electrodesInsertionOrIntercalationOn the contrary, lithium goes outExtractionorDeintercalationCalled.In the battery, lithium exits the positive electrode and enters the negative electrode during charging.On the contrary, at the time of discharge, lithium exits from the negative electrode and enters the positive electrode.Electrons flow to an external circuit during operation.
The half-reaction at both poles is as follows.
- Positive electrode:
- Negative electrode:
The overall reaction is limited. Over-discharging of lithium cobalt oxide leads to the formation of lithium oxide.. The following reactions are observed.
X-ray analysis confirms that cobalt (IV) oxide is generated by overcharging above 5.2 V.
In the lithium-ion battery, lithium ions are transported to the negative electrode and the positive electrode, and metal orLixCoO2The cobalt inside is chargedCo3+からCo4+Is oxidized to dischargeCo4+からCo3+Is reduced to. In secondary batteries including this battery in general, the anode reaction (oxidation reaction) takes place at the positive electrode during charging, but the positive electrode is the cathode (Cathode) and the negative electrode is the anode (Anode). Often fixedly called.
Lithium ion secondary batteryThe cost of the rare elements used in the cathode materialcobaltOccupy 7% of that, but in recent years, with the aim of significantly lowering the cost, positive electrode materials have been selected.manganese,nickel,Iron phosphateThose that use etc. are being developed. (Nickel is a rare element but cheaper than cobalt. Manganese is a rare metal commercially, but it is not strictly a rare element.).
|Cathode material||Average voltage||Capacity per weight||Energy per weight|
|LiCoO2||3.7 V||140 mA · h / g||0.518 kW ⋅ h / kg|
|LiMn2O4||4.0 V||100 mA · h / g||0.400 kW ⋅ h / kg|
|LiNiO2||3.5 V||180 mA · h / g||0.630 kW ⋅ h / kg|
|lifepo4||3.3 V||150 mA · h / g||0.495 kW ⋅ h / kg|
|Li2FePO4F||3.6 V||115 mA · h / g||0.414 kW ⋅ h / kg|
|LiCo1/3Ni1/3Mn1/3O2||3.6 V||160 mA · h / g||0.576 kW ⋅ h / kg|
|Li (LiaNixMnyCoz)O2||4.2 V||220 mA · h / g||0.920 kW ⋅ h / kg|
Negative electrode material
When Sony began commercial production of lithium-ion secondary batteries around 1990,GraphiteRather, it is obtained by firing a polymer whose graphite crystal structure is difficult to develop.Hard carbonWas used.
Regarding the discharge characteristics of graphite and hard carbon, graphite is almost smooth and flat from the beginning of discharge to the end of discharge.VoltageIn contrast to hard carbon, the voltage drops sharply at the end of discharge, whereas in the case of hard carbon, the voltage drops uniformly to the discharge end voltage.
Therefore, in the case of hard carbon, the capacity of the battery can be directly and accurately known by measuring the voltage, but there is a drawback that the battery voltage is not stable. On the other hand, in graphite, since the voltage change is small, it is not possible to know the battery capacity from the battery voltage, but there is an advantage that a high voltage is stably maintained until the end of discharge.
Although the one using hard carbon has the advantage that it has a cycle characteristic of more than 1000 times, it cannot obtain a uniform voltage as it is, so it is necessary to boost the voltage with a DC-DC converter in the low voltage region. Therefore, the peripheral circuit becomes expensive, and at present, the hard carbon type battery is used only for some devices. Further, tin and silicon materials have begun to be put into practical use as next-generation materials replacing graphite and hard carbon. It has been known that these materials show a capacity several times to several tens times that of graphite due to an alloying reaction with lithium, but it is difficult to prolong the life due to a large volume change. Currently, it has both capacity and life by combining with carbon materials.
ToshibaIs an oxide material instead of a carbon material for the negative electrode material.Lithium titanate We are developing a lithium-ion secondary battery "SCiB" that uses (LTO), which is said to have high safety, excellent low-temperature characteristics, and capable of approximately 6,000 charge/discharge cycles..
|Negative electrode material||Average voltage||Capacity per weight||Energy per weight|
|Graphite (LiC6)||0.1–0.2 V||372 mA · h / g||0.0372–0.0744 kW · h/ kg|
|Hard carbon (LiC6)||? V||? mA · h / g||? kW · h / kg|
|Titanate (Li4Ti5O12)||1–2 V||160 mA · h / g||0.16–0.32 kW ⋅ h / kg|
|Si (Li4.4Si)||0.5–1 V||4212 mA · h / g||2.106–4.212 kW ⋅ h / kg|
|Ge (Li4.4Ge)||0.7–1.2 V||1624 mA · h / g||1.137–1.949 kW ⋅ h / kg|
Aqueous electrolyte cannot be used because it is electrolyzed by lithium, and non-aqueous electrolyte is used... The liquid electrolyte in the lithium-ion batteryLiPF6,LiBF4OrLiClO4And a solvent such as ethylene carbonate. The liquid electrolyte is filled between the positive electrode and the negative electrode, and lithium ions move by charging and discharging. Generally at room temperature (20 ° C) Is the conductivity of the electrolyte 10 mS/cm (1 S/m) so 40 ° CThen about30% –40%で0 ° CFurther down in the vicinity.
However, the organic solvent easily decomposes and deteriorates at the positive electrode. Despite the use of suitable organic solvents for the electrolyte, the solvent essentially decomposes into a solid layer called the interphase solid electrolyte (SEI)... This hinders the conductivity of lithium ions. Prevents decomposition of electrolyte after charging between phases. As an example, ethylene carbonate is better than lithium0.7 VIt decomposes at high voltage, has a high density, and is stable between phases.
Manufacturing process overview
The positive electrode is manufactured by applying an active material solution such as lithium cobalt oxide on both sides of an aluminum foil, drying it, and then pressing it to increase its density. The negative electrodecopperAfter applying a solution of carbon material etc. to the foil and drying it, press it to increase the density and manufacture.
The electrode material is intermittently applied to the electrode foil manufactured in the shape of a long strip in a lateral stripe shape, and cut according to the size and shape of the battery as a product. Of these, the portion to which the electrode material is not applied is the portion to which the connection terminal (tab) for inputting/outputting electric power is welded. An aluminum tab is used for the positive electrode and a nickel tab is used for the negative electrode.
A porous insulating film that allows ions to move is sandwiched between the negative and positive electrodes,BaumkuchenWrap the positive electrode, the negative electrode, and the insulating film so that they overlap each other.
If the battery has a cylindrical shape, the electrode will be rolled into a cylindrical shape.nickelplatingIt is put in a steel can. After welding the negative electrode to the bottom of the can and injecting the electrolyte, the positive electrode is welded to the lid (top cap) and sealed with a press like a can of food.
In the case of a prismatic battery, the electrode is wound into a flat shape in accordance with the can, and the positive electrode is welded to the aluminum outer can. Also, in the case of a square type, it is sealed by laser welding.
After the battery is assembled, the battery is activated by charging in the activation process, and charging, discharging, aging at room temperature, aging at high temperature, etc. are repeated several times, and screening for battery selection is performed before shipment.
Cylindrical battery size
The standard (size) of the cylindrical lithium ion secondary battery is the diameter (mm2 digits in unit + length (0.1 mmIt is represented by a total of 3 digits (5 digits in units). As of 2013, there are 26650/18650/17670/18500/18350/17500/16340/14500/10440 standards for cylindrical batteries on the market. The 14500 is the size equivalent to a so-called AA dry battery, and the 10440 is the size equivalent to a AAA dry battery.
- High energy density
- Currently in practical useSecondary batteryHas the highest energy density of
- Weight energy density (100-243 Wh/kg) isNickel hydride battery(60-120 Wh/kg) twice,Lead acid battery30 times (40-5 Wh/kg) and lighter.
- The volumetric energy density (250-676 Wh/L) is 140 times that of nickel-hydrogen batteries (300-1.5 Wh/L) and 60-75 times that of lead-acid batteries (4-5 Wh/L), and can be made smaller.
- High voltage of 4 V class
- Conventional rechargeable batteriesElectrolyte Ofsolvent Wed(Aqueous solution), so when a voltage of 1.5 V or higher is applied,hydrogenとoxygenToElectrolysisI have done it,Organic solventIt was possible to obtain an electromotive force higher than the electrolysis voltage of water by using.
- Nominal voltage (3.6-3.7 V) is 1.2 times that of nickel hydrogen battery (3 V), 2.1 times that of lead acid battery (1.5 V),Dry cellThis is 1.5 times that of (2.5 V), and when a high voltage is required, the number of batteries used in series can be reduced.
- Memory effectThere is no
- Since there is no phenomenon (memory effect) that the capacity of the battery itself decreases due to repeated shallow charging and discharging, it is possible to add and charge at any time.NiCd batteryAnd this always happens with nickel metal hydride batteries.
- Self-dischargeLess is
- About 5% of the phenomenon (self-discharge) that discharges spontaneously little by little if left unused for a while is similar to that of NiCd or NiMH batteries. 1⁄5 And much better.
- Good charge/discharge efficiency
- The ratio of the amount of electricity obtained by discharging to the amount of electricity required for charging (charging/discharging efficiency) is 80%-90%, which is a relatively small electrical loss, and is therefore suitable for power storage applications.
- Long life
- Withstands more than 500 charge/discharge cycles and can be used for a long time. It can be used 1000 times or more if used properly. However, in recent years, the number "500 times" has become a mere mess. At present, with higher capacity and increased output current, low values are obtained when subjected to JIS cycle tests, so many products do not receive JIS and describe their own values.
- Fast charging is possible
- Recently, products that can charge 3C have also appeared. (About 1C for general type)
- Large current discharge possible
- It was thought that it was not suitable for high current discharge, but it has been overcome by improvement. Large industrial products that can discharge a large current of several hundred A have also appeared..
- Wide operating temperature range
- The general type can be used in a wide temperature range of -20-60℃ (0-45℃ when charging). Unlike dry batteries, it does not use an aqueous solution as an electrolyte, so it can be used in sub-zero temperatures. Although the capacity increases as the temperature rises within the guaranteed temperature, deterioration occurs when left at high temperature, and the discharge capacity remarkably decreases at low temperature.
- High versatility
- The overall performance is well balanced (there are few drawbacks), so it can be used for various purposes from mobile phones to automobiles. A secondary battery that has better performance than a lithium-ion battery if it has only one of performance such as capacity and charging speed has been reported, but if the other performance is not good at the same time, it will not be widely used so far.
The normal area and the dangerous area are very close to each other, and a protection circuit for monitoring charge / discharge must be provided to ensure safety.This is because when the voltage rises during charging, the positive electrode and the negative electrode are placed in an extremely strong oxidizing / reducing state, and the material is more likely to become unstable than other low-voltage batteries.
If the battery is charged rapidly or excessively, heat is generated on the positive electrode side due to oxidation of the electrolyte and destruction of the crystal structure, and metallic lithium is deposited on the negative electrode side. This connects the two poles directly, and the circuitシ ョ ー トResulting in. Not only will the battery deteriorate rapidly, but in the worst case, it may explode or catch fire... Therefore, in charging, extremely high accuracy (tens of mVVoltage control is required.
In over discharge,cobaltMay be eluted or the negative electrode current collectorcopperWill be eluted and will not function as a secondary battery. In this case also, abnormal heat generation of the battery will occur. Lithium cobalt oxideFlammabilityHigh and included in the battery once it burns upOxidantIt's hard to touch because it burns into.
Because of the high energy density,Short circuitSometimes there is a big risk of sudden overheating,Organic solventThe electrolyte solution may volatilize and cause a fire accident. A short circuit may occur inside the battery when an external force is applied, and it is necessary to protect it from impact.
If the temperature becomes too high, there is a risk of explosion, fire and explosion due to thermal runaway.
The storage characteristics (performance retention characteristics in storage) are inferior to those of nickel hydrogen batteries. Further, when stored in a fully charged state, the deterioration of the battery rapidly progresses. For this reason, it is a common charging method for other storage batteries.Trickle chargeIs not suitable for lithium-ion batteries. In addition, because of high heat generation characteristics, control circuit and protection circuit essential, high voltage per cell, etc.,Dry cellIt is unsuitable for the alternative use of and is not popular. (Nickel/hydrogen rechargeable battery#OutlineSee also)
Safety and measures
Since the lithium ion secondary battery does not use metallic lithium, it can be charged and discharged more safely than the lithium secondary battery. However, there are various risks in the lithium ion secondary battery, which can be said to be the inside out of the high energy density. Since it is also an essential problem, various safety measures have been taken for the battery itself and its peripheral circuits. These safety measuresPatent BulletinIt can be found by
In spite of these measures, abnormal overheating and ignition are often reported in notebook computers and mobile phones. In some cases, problems in the manufacturing process were suspected, leading to large-scale collection. For specific examples of accidentsAbnormal heat generation problem of lithium-ion secondary batterychecking ...
In 2020, Toshiba developed a new lithium-ion battery with less risk of ignition or explosion...It is characterized by using a non-burning aqueous solution for the electrolytic solution that fills the space between the electrodes..
Commercially available form
Depending on how it is used, there is a risk of fire and explosion.Battery packThe product of a single battery cell such as a manganese battery or an alkaline battery is not commercially available.Radio controlAs a power source for hobby use, etc., a product without an electronic safety circuit is commercially available, but it is supposed to be used in an expensive dedicated charger/discharger, and is housed in a strong case.
Exceptionally, electronic parts specialty stores sell battery cells to the general public, but it is dangerous to use them without taking protection circuits or short-circuit prevention measures. Also, it is very dangerous for the user to disassemble the battery pack.
Webshops in Japan sell products made in Japan and overseas with built-in electronic safety circuits and products without electronic safety circuits. Mainly 18650/17650/14500/10440 etc. can be obtained as a single battery cell for around 1 yen to 900 yen.
When the temperature rises due to an internal short circuit, etc. and the internal pressure rises, a safety valve with a current cutoff function is built in to prevent an explosion. This safety valve is located on the convex portion of the positive electrode, and releases the gas to the outside when a certain pressure or more is applied. In addition, the internal resistance of the top cover of the cylindrical battery increases as the temperature rises.PTC elementIs built in, and has a structure that electrically interrupts the current when the temperature rises.
- Put a stainless steel pin in the center of the battery element to increase the strength against bending of the can
- For electrode tabs and tab attachmentsInsulating tapePrevent internal short circuit from the edge of the pasted tab
- Insulation tape is attached to the entire winding start and end of the electrode to prevent dendrites from forming. (Dendrite formation may be caused not only by lithium metal, but also by the precipitation of impurities such as zinc in aluminum foil. is there)
- Applying fine ceramic powder to part or almost all of the electrode or separator to increase the strength of the insulating layer.
Manufacturers are trying to ensure safety by using various methods such as.
The overcharge control of the charging voltage is managed not only by the charger but also by the control circuit in the battery pack. Further, for over-discharge, the control circuit in the battery pack shuts off the output before reaching the over-discharge state.
Loss of superiority
The advantage of the lithium-ion secondary battery was the overwhelming high energy density over the nickel-hydrogen secondary battery, and the performance sufficient to accept the risk. However, the lithium ion2000 eraNickel-hydrogen, which was able to devote development resources to high performance while taking measures against a series of abnormal heat generation and ignition problems that occurred in the very beginning, has a volume ratio of 1/2 and a weight ratio of The performance difference has been reduced to 1/3, the level at which direct comparison is possible. Originally it was not a strong weak point like NiCad batteriesMemory effectIn addition, technology for further suppressing is being developed. Although the nickel-hydrogen secondary battery is structurally difficult to be extremely miniaturized, the market for lithium-ion batteries is still secured, but on the other handDry cell(Primary battery) Compatible rechargeable batteries, where nickel-metal hydride batteries are currently the mainstream, it is becoming impossible for lithium-ion batteries to replace them.[Source required].
Next-generation secondary battery
Improved poor overcharge characteristics of lithium-ion secondary batteriesLithium ion polymer secondary batteryHas been developed and has been put to practical use in some areas. In addition, as a positive electrode material, LiNiO2, LiMn2O4 As the negative electrode material, a material using tin or an alloy of silicon and lithium has also been studied.
Although it is still out of the idea, "calcium"Ion batteries" are also being researched (different from the calcium electrode batteries used in general passenger cars, commonly known as "MF batteries"). This battery has a slightly lower battery voltage than a lithium-ion battery (theoretical voltage is fully charged)3.5 VDegree), but lithium ion 1 mol When exchanging 1 mol of calcium ions between the two electrodes, the current density is doubled (because it is divalent). For electrolyte Ca (ClO4)2,Ca2[Fe (CN)6] A solution obtained by dissolving the above in an aprotic polar solvent is used. As electrode materialCaMn2O4/not2The system looks promising. others,magnesium,sodiumI also have an idea to use.
Aqueous lithium ion battery
In conventional lithium-ion batteries, the electrolysis voltage of 1.23 V or higher, which is the electrolysis voltage of water, requires the use of flammable, toxic, and expensive non-aqueous electrolytes.Aqueous solutionSystem electrolyte (Ionic liquid) Is being developed, a lithium-ion battery is being developed. Several methods have been proposed, one using a two-component high-concentration electrolyte ``water-in-bisalt'' (WiBS) and the other usingIonic liquidEach method has advantages and disadvantages. When using WiBS, hydrogen is generated below 0.5 V (vs. Li/Li+), so general LiB electrodes cannot be used.GraphiteA method is proposed to prevent the electrolysis of water by forming a protective film on the negative electrode or the lithium metal surface..
Aqueous systemElectrolyteBy using, the thoroughness of 0% humidity was indispensable in the manufacturing process of the conventional non-aqueous electrolyte lithium-ion battery.DehumidificationSince it is not necessary, it is expected that the working environment can be improved and the cost can be reduced, the risk of ignition etc. can be reduced, and the safety can be improved..
Nanowire batteryIs a type of lithium-ion rechargeable battery in 2007Stanford UniversityInvented by Yi Cui. His team's invention was to replace the conventional graphite anode with silicon.Nano wireIt is replaced with a stainless steel negative electrode covered by. Since silicon stores 10 times as much lithium as graphite, the energy density at the negative electrode is much improved and the volume of the rechargeable battery can be reduced. Since the surface area is large, charging/discharging becomes faster.
Silicon negative electrodes have been studied (partially put into practical use) because they have a capacity that greatly exceeds conventional carbon-based negative electrodes.IntercalationSince silicon swells to several times its volume due to (), cracks are likely to occur, and deterioration (capacity reduction) is likely to occur when charging and discharging are repeated, which is a problem.
It is known that nano-sized materials generally increase flexibility with respect to volume change. For this reason, almost all silicon-based negative electrodes currently being researched contain silicon.NanoparticlesIt has become a structure in which it is connected with conductive carbon. On the other hand, the silicon nanowire-based negative electrode developed by Dr. Cui's group at Stanford University uses a very long nanowire as an electrode to smooth the flow of electrons to the end of the electrode, and deterioration due to volume change is caused by the wire. It was avoided because it had a nano-sized diameter, and because of its extremely large surface area, it was easy for Li ions to enter, enabling high-speed charging and discharging. According to their experimental results, the initial capacity is 10 times that of the existing carbon-based negative electrode, and the capacity is 8 times that of the subsequent charge/discharge..
Note that his group continued toNano materialWe are developing electrodes usingNano wireProduces sulfur covered with scaly carbon and reports its excellent properties as a positive electrode material.. Sulfur cathode is currently usedLiCoO2,lifepo4It is possible to realize a capacity (per unit weight) that is about 10 times that of a positive electrode material, and especially the development by Korean manufacturers is proceeding, but the problem is that the cycle characteristics are poor and it rapidly deteriorates due to charging and discharging. Has become. Their carbon-coated sulfur nanowire positive electrode improves cycle characteristics by preventing the sulfur from leaching because it is covered with carbon, and has a very large capacity of 150 mAh/g even after about 700 charge/discharge cycles. Has been maintained.
However, it is still difficult to apply these well-controlled nanostructures to batteries in the mass production stage, and these technologies are not immediately available on the market as products.
The nanoball battery has the same idea as the nanowire battery, and by making the material of the electrode nanosize,IntercalationIncreases flexibility to change volume with temperature, improves power density and cycle characteristics.. Although it is expected that ultra-high speed charge/discharge will be possible, there are many problems and it is difficult to fix many nanoballs as electrodes.IntercalationIt has been pointed out that it will be deteriorated due to the volume change due to, and as of 2018, there is no prospect of mass production.
Lithium iron phosphate battery
Fewer resource restrictions than the format that uses cobalt for the positive electrode materialIt has a wide safety area and does not easily ignite even with nails.Since it is relatively safer than lithium-ion batteries that use other positive electrode materials, it has expanded its share in recent years. Representative manufacturers are A123 Systems, Changs Ascending Enterprise Co., Ltd. (CAEC), China Sun Group and BYD. The iron phosphate lithium-ion battery has different characteristics from the conventional lithium-ion battery. Compared to competing lithium-ion cobalt ion batteries, the dischargeable current is less, but there are cases where the dischargeable current was improved by substituting some elements of lithium iron phosphate..
Lithium iron phosphate battery has the following features
- Storage capacity per unit volume is less than lithium cobalt oxide battery.
- Many lithium iron phosphate batteries have lower discharge rates than lead acid batteries and lithium cobalt oxide batteries. A lithium iron phosphate battery has a lower voltage and a lower energy density than a lithium cobalt oxide battery, but has excellent cycle life. This drawback is due to the lithium ion cobalt oxide batteryLiMn2O4Can be offset by longer life and slower capacity reduction than lithium-ion batteries, lithium polymer batteries, etc..
Example: Lithium iron phosphate batteries and lithium cobalt oxide batteries have approximately the same energy density after one year.
- Voltage Minimum discharge voltage = 2.8 V.Operating voltage = 3.0–3.3 VMaximum charging voltage = 3.6 V.
- Energy per unit volume = 220 Wh / dm3 (790 kJ / dm3)
- Energy per weight =>90 Wh / kg (> 320 J / g)
- 100% depth of discharge (DOD) cycle life (some up to 80% of original capacity) = 2,000-7,000 
- Cathode composition (weight ratio)
- 90% C-lifepo4, Grade Phos-Dev-12
- 5% carbon EBN-10-10 (stratified graphite)
- 5% PVDF
- Cell specifications
- Test conditions: ** The following conditions were changed from a lithium ion cell using cobalt as the cathode to lithium iron phosphate.
- room temperature
- Limit voltage: 2.5–4.2 V
- Charge: from C/4 4.2 V, When the potential 4.2 V From I <C / 24
Safety of lithium iron phosphate batteries
lifepo4Originally the positive electrode materialLiCoO2Safer than manganese spinel.. The Fe-PO bond is stronger than the Co-O bond. Therefore, it is difficult for oxygen atoms to be released even when a short circuit or overheating occurs. The stability of this redox energy assists the transfer of ions. (800 ° CJust burn down under heating (above)LiCoO2Can undergo thermal runaway under similar conditions, while the stability of the bond reduces its risk.
LithiumLiCoO2By coming out from the positive electrode of the battery, CoO2Undergoes non-linear expansion which affects the structural integrity.lifepo4Similarly, due to the ingress and egress of lithium, the structure is similarly affected.lifepo4The battery isLiCoO2It has a more stable structure than batteries.
When fully chargedlifepo4The battery has no lithium in the positive electrodeLiCoO2In the case of batteries, about 50% remains in the positive electrode.
In 2012, adopted lithium iron phosphate batteryElectric car,BYD ・ e6 Traffic accidentCaused a flame. BYD executives have suggested that lithium-ion batteries may have contributed to the cause of the flame.
In 1993Nippon Telegraph and Telephone From (NTT)University of TexasAn employee dispatched to John Goodenough's laboratory as a researcher leaked confidential information about a lithium iron phosphate battery to his work place against a contract for confidentiality, and in November 1995, NTT secretly patented it. I applied for it and started selling it to a Japanese electronics manufacturer.
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