CN102780041A - Overcharge prevention electrolyte for lithium ion batteries - Google Patents
Overcharge prevention electrolyte for lithium ion batteries Download PDFInfo
- Publication number
- CN102780041A CN102780041A CN2012102659870A CN201210265987A CN102780041A CN 102780041 A CN102780041 A CN 102780041A CN 2012102659870 A CN2012102659870 A CN 2012102659870A CN 201210265987 A CN201210265987 A CN 201210265987A CN 102780041 A CN102780041 A CN 102780041A
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- electrolyte
- battery
- additive
- additives
- lithium ion
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to an overcharge prevention electrolyte for lithium ion batteries. The overcharge prevention electrolyte is characterized by being composed of electrolyte solute and additives, wherein the electrolyte solute is formed by one or several of LiClO4, LiAsF6, LiBF4, LiCF3SO3, LiBOB and LiPF6, the additives are formed by one or several of sulfurous acid vinyl ester, sulfurous acid propylene ester, biphenyl, vinylene carbonate, ring ethyl benzene, acetic acid vinyl ester, hydrogenated dibenzofuran, vinyl cyanide, xylol, uni-fluoromethyl ethylene carbonate, bi-fluoromethyl ethylene carbonate and 3-butyl phosphate, and the additives occupies 0.1-3% of the electrolyte solute by weight. The overcharge prevention electrolyte is needed to be combined with a positive temperature coefficient (PTC) element in use, the use amount of the additives is reduced as far as possible under the premise of achieving the purpose of overcharge prevention by optimizing the use amount of the electrolyte additives, so that effects of reducing cost and reducing performance loss of the electrolyte as far as possible can be achieved.
Description
Technical field
The present invention relates to a kind of lithium ion battery with the anti-electrolyte that overcharges.
Background technology
Lithium ion battery has that capacity is big, operating voltage is high, retention of charge is strong, has extended cycle life, pollution-free, memory-less effect, specific energy advantages of higher; Be widely used in various electronic equipments, like notebook computer, mobile phone, digital camera, portable lighting equipment etc.Simultaneously, it also is used to electric tool, electric bicycle and electric automobile.Along with the consumption gradually of world petroleum resource, and the society requirement on environmental protection is improved gradually, electric motor car and energy storage have obtained unprecedented opportunity to develop with battery, the application of lithium ion battery is also constantly being widened.
Electrolyte is the important component part of battery, is bearing and is passing through inside battery transmits ion between positive and negative electrode effect, and it has significant effects to capacity, operating temperature range, cycle performance and the security performance etc. of battery.Electrolyte generally is divided into two types of liquid electrolyte and solid electrolytes, needs to satisfy following basic demand: the ionic conductivity that (1) is high generally should reach 1 * 10
-3～2 * 10
-2S/cm; (2) high thermal stability and chemical stability do not decomposed in wider temperature range; (3) electrochemical window of broad keeps the stable of chemical property in the voltage range of broad; (4) has good compatibility with other part of battery; (5) safe, nontoxic, pollution-free.
The liquid organic electrolyte is the most commonly used, but along with the range of application of battery is constantly widened, people constantly increase the requirement of battery each side, and original electrolyte system can not satisfy instructions for use.In electrolyte, add a spot of some material, can significantly improve some performance of battery, like the security performance of the cycle efficieny of the conductivity of electrolyte, battery and reversible capacity, battery etc., these small amount of matter are called functional additive.Generally need in electrolyte, add some specific function that some functional additive is realized battery, functional additive is applied more and more in the production of battery and research.
Battery in use safety is primary all the time; Overcharging is an important index; Generally, also improve from the aspects such as electrolyte of battery design and battery except in the battery pack process of assembling, improving the safety through peripheral security set and protective circuit plate.Utilize electrolysis additive to realize that the over-charge protective of battery has very important significance with reducing cost for simplifying battery manufacturing process, generally can consider from the following aspects: 1 redox shuttle, 2 fire-retardant electrolyte, 3 self closing additive agent electrolytes.
Add the fail safe that anti-overcharging additive can effectively improve battery in the electrolyte, but additive is not The more the better, does not overcharge qualifiedly just can guarantee that other project is outstanding too as long as be.The addition of anti-overcharging additive too much can influence other performances of battery, reduces like battery capacity, and circulation variation, safety test bulging exceed standard etc.Therefore; The use of general additive will reduce under situation about being effective as far as possible, and in order to obtain good effect, the single result of use that different additive has is good; What have then needs compound use better, and the kind of additive and addition remain to be scrutinized.In addition, for the adding that reduces additive to the influence that other performance of battery causes, the form that can adopt multiple mode to combine reduces the use amount of additive when improving over-charging.
Summary of the invention
The purpose of this invention is to provide a kind of lithium ion battery and overcharge electrolyte, adopt this electrolyte can make battery change the anti-over-charging that significantly improves battery under the little situation in electrical property, environmental performance with anti-.
A kind of lithium ion battery overcharges electrolyte with anti-, and its special feature is: be made up of electrolyte and additive, wherein the electrolyte solute is LiClO
4, LiAsF
6, LiBF
4, LiCF
3SO
3, LiBOB and LiPF
6In one or more; And additive is in ethylene sulfite, propylene sulfite, biphenyl, vinylene carbonate, ring ethylo benzene, vinyl acetate, hydrogenated dibenzofurans, acrylonitrile, xylenes, a fluoro methyl carbonic acid vinyl acetate, two fluoro methyl carbonic acid vinyl acetate and the 3-butyl phosphoric acid ester one or more, and its addition is the 0.1-3% of electrolyte by weight.
Wherein electrolyte adopts LiPF
6Electrolyte, and additive is BP and CHB, wherein the addition of BP is the 0.1%-0.5% of electrolyte quality, the addition of CHB is the 0.5%-1% of electrolyte quality.
Wherein electrolyte adopts LiPF
6Electrolyte, additive are BP and CHB, and wherein the addition of BP is the 0.5%-1% of electrolyte weight, and the addition of CHB is the 1%-2% of electrolyte quality.
The invention provides the anti-solution that overcharges of a kind of lithium ion battery safe and reliable, simple for process, that production cost is low.Electrolyte of the present invention need combine the use of PTC (positive temperature coefficient element); Through optimizing the use amount of electrolysis additive; Reach the use amount that reduces additive under the anti-prerequisite that overcharges target as far as possible, reducing cost, reducing as far as possible the effect of other performance loss to reach.
Embodiment
Electrolyte of the present invention (containing additive) combines the double action of PTC, can significantly improve the anti-over-charge safety performance of battery, can guarantee basically to test through the harshest test-1C20V that overcharges.If content of additive increases again, possibly under the effect that does not need PTC, can test, but other performance of battery can obviously descend through the common test-3C4.5V that overcharges.Therefore, core of the present invention is through overcharging the composite action of electrolyte and PTC, overcharging in raising and realize the combination property that battery is maximum under the safe prerequisite.
New electrolyte process of the test of the present invention is following:
(1) test is prepared:
Get assemble in advance treat 80 of intercells, put into vacuum drying oven and dry, to guarantee after the oven dry that the moisture of inside battery all is discharged from.
Preparing electrolyte, whole process need carries out in dry environments such as drying room or glove box, and original electrolyte is commercial li-ion battery electrolytic solution commonly used, and the used in amounts of electrolyte adds 50% surplus again on the basis of theoretical amount of calculation.The electrolyte that takes out is divided into the quartering, is designated as electrolyte one, electrolyte two, electrolyte three, electrolyte four successively.Add anti-overcharging additive in three parts of electrolyte backward, content of additive is grown out of nothing, is increased successively in four parts of electric liquid.The electrolyte for preparing is fully rocked, guarantee that additive evenly scatter in electrolyte, after shaking up it is kept in the dry environment, wait for fluid injection.
(2) fluid injection test:
The fluid injection all processes requires in the environment of drying, to carry out (in drying room or the glove box), and last hour battery with oven dry of fluid injection takes out from drying box and leave in the dry environment.Fluid injection uses dropper or syringe to carry out, and need employed utensil be cleaned with organic solvent before the fluid injection, dries up.Need on balance, confirm to require the volume sign of electric liquid measure before the fluid injection, to make things convenient for follow-up work.
Fluid injection is carried out according to the order of electric liquid one, electric liquid two, electric liquid three, electric liquid four successively, 20 of every kind of electric liquid fluid injections.Fluid injection is accomplished in two steps, injects most of electrolyte first, battery is placed in the dry environment leaves standstill then, leaves standstill and finishes laggard line precharge exhaust.Carry out the secondary fluid injection after exhaust finishes, the residual electricity liquid that the secondary fluid injection needs not reach design load is supplied, and after supplying battery is done to seal and handles and clean up.
(3) change into, test:
The battery of having annotated liquid done leave standstill processing, change into then, carry out burin-in process after changing into, the essential information of test record battery is tested according to the battery that the essential information selection mode is good then.Three projects are mainly done in test: high temperature circulation, floating charge and overcharge, and wherein high temperature circulation is done 10 circulations at 70 ℃; The floating charge test kept constant voltage charge 15 days at 45 ℃ of constant current charges to 4.25V; Overcharge test and need weld PTC, do the 1C20V test.Require each project to make at least three batteries, verify the effect of additive then according to test result.
The original electrolyte that uses of dosing stage of the present invention is dissolved in the solution that polynary organic solvent forms as among LiClO4, LiAsF6, LiBF4, LiCF3SO3, LiBOB or the LiPF6 one or more.
The present invention uses that additive that electrolyte adds is stupid as ethylene sulfite, propylene sulfite, biphenyl, vinylene carbonate, ring ethyl, in vinyl acetate, hydrogenated dibenzofurans, acrylonitrile, xylenes, a fluoro methyl carbonic acid vinyl acetate, two fluoro methyl carbonic acid vinyl acetate, 3-butyl phosphoric acid ester etc. one or more, and addition is 0.1-3%.
Test that the present invention overcharges need have PTC to be carried out, and additive therefor content promptly of the present invention needs to unite use with PTC, the convenient like this use amount that further reduces additive, and raising overcharges and makes that other performance reduction of battery is less safe the time.
The present invention need pass through three test optimization additive formulations; High temperature circulation needs the capacity and the cycle performance of fast detecting battery; And guarantee lower high temperature bulging rate; Floating charge will guarantee further that safety and the bulging distortion of battery is little, overcharges then and need under the situation that satisfies above-mentioned two kinds of detections, guarantee to overcharge safety.
Embodiment 1:
Get assemble in advance treat 20 of intercells, put into vacuum drying oven and dry, guarantee that the moisture of inside battery all is discharged from, preceding 1 hour of fluid injection battery is taken out and leaves standstill.Take by weighing general commercial LiPF at drying room
6Electrolyte 80g adds BP0.25g in the electrolyte that takes by weighing, CHB0.8g shakes up electrolyte, guarantees that additive evenly disperses in electrolyte, obtains electrolyte two.
The electrolyte for preparing two is carried out fluid injection, and every fluid injection for the first time is 2.5g, puts into vacuum tank after having annotated and vacuumizes and impel electrolyte to soak into fast; Then battery is left standstill, carry out pump-down process, after the exhaust electrolyte two is carried out the secondary fluid injection; Every fluid injection 0.5g; Equally battery is put into vacuum tank and vacuumize, after the fluid infusion battery is sealed, and clean up and obtain sample B.
Battery after the fluid injection left standstill carry out formation charging two days later, aging then, battery is carried out 70 degree high temperature circulation tests, 45 degree floating charges tests and overcharges test after aging.The essential information of recording cell before the test, every kind of test is selected 4 qualified samples and is tested, and test result is got its mean value, is designated as B1 (70 degree loop test result), B2 (45 degree floating charge test result), B3 (overcharging test result) respectively.
Comparative Examples 1:
Get assemble in advance treat 20 of intercells, put into vacuum drying oven and dry, guarantee that the moisture of inside battery all is discharged from, preceding 1 hour of fluid injection battery is taken out and leaves standstill.
Take by weighing general commercial LiPF at drying room
6Not doping of electrolyte 80g (electrolyte one) is carried out a fluid injection with electrolyte one, puts into vacuum tank after having annotated and vacuumizes and impel electrolyte to soak into fast; Then battery is left standstill; Carry out pump-down process, carry out the secondary fluid injection after the exhaust, equally battery is put into vacuum tank and vacuumize; After the fluid infusion battery is sealed, and clean up and obtain sample A.
Battery after the fluid injection left standstill carry out formation charging two days later, aging then, battery is carried out 70 degree high temperature circulation tests, 45 degree floating charges tests and overcharges test after aging.The essential information of recording cell before the test, every kind of test is selected 4 qualified samples and is tested, and test result is got its mean value, is designated as A1 (70 degree loop test result), A2 (45 degree floating charge test result), A3 (overcharging test result) respectively.Though the sample of Comparative Examples 1 does not have additive, its electrical property is better than embodiment's 1, not through overcharging test, has potential safety hazard basically.
Comparative Examples 2:
The experimental procedure of Comparative Examples 2 is with embodiment 1; Different is that additive level is BP0.4g in the electrolyte; CHB0.8g (electrolyte three) is designated as C with the sample that makes, and test result is designated as C1 (70 degree loop test result), C2 (45 degree floating charge test result), C3 (overcharging test result) respectively.All through overcharging test, its electrical property has certain decline than embodiment 1 to the sample of Comparative Examples 2 under extreme test, but can not cause tangible influence to normal use basically.
Comparative Examples 3:
The experimental procedure of Comparative Examples 3 is with instance 1; Different is that additive level is BP0.8g in the electrolyte; CHB1.6g (electrolyte four) is designated as D with the sample that makes, and test result is designated as D1 (70 degree loop test result), D2 (45 degree floating charge test result), D3 (overcharging test result) respectively.Content of additive increases in Comparative Examples 3 electrolyte, and its sample is all through overcharging test, but electrical property is more than the decline of embodiment 1 under extreme test, may cause influence slightly to practical application.
1.70 degree high temperature circulation test (10 times)
| Sample | Average circulation volume | Thickness before the test | Test back thickness | The bulging rate |
| A1 | 1165 | 5.4 | 5.51 | 2.04％ |
| B1 | 1158 | 5.41 | 5.82 | 7.58％ |
| C1 | 1145 | 5.4 | 5.91 | 9.4％ |
| D1 | 1140 | 5.43 | 6.1 | 12.34％ |
2. floating charge test
3. overcharge test (√ passes through, * through)
The contrast test result is as implied above.
Claims (3)
1. a lithium ion battery overcharges electrolyte with anti-, and it is characterized in that: be made up of electrolyte and additive, wherein the electrolyte solute is LiClO
4, LiAsF
6, LiBF
4, LiCF
3SO
3, LiBOB and LiPF
6In one or more; And additive is in ethylene sulfite, propylene sulfite, biphenyl, vinylene carbonate, ring ethylo benzene, vinyl acetate, hydrogenated dibenzofurans, acrylonitrile, xylenes, a fluoro methyl carbonic acid vinyl acetate, two fluoro methyl carbonic acid vinyl acetate and the 3-butyl phosphoric acid ester one or more, and its addition is the 0.1-3% of electrolyte by weight.
2. a kind of lithium ion battery as claimed in claim 1 overcharges electrolyte with anti-, it is characterized in that: wherein electrolyte adopts LiPF
6Electrolyte, and additive is BP and CHB, wherein the addition of BP is the 0.1%-0.5% of electrolyte quality, the addition of CHB is the 0.5%-1% of electrolyte quality.
3. a kind of lithium ion battery as claimed in claim 1 overcharges electrolyte with anti-, it is characterized in that: wherein electrolyte adopts LiPF
6Electrolyte, additive are BP and CHB, and wherein the addition of BP is the 0.5%-1% of electrolyte weight, and the addition of CHB is the 1%-2% of electrolyte quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102659870A CN102780041A (en) | 2012-07-30 | 2012-07-30 | Overcharge prevention electrolyte for lithium ion batteries |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102659870A CN102780041A (en) | 2012-07-30 | 2012-07-30 | Overcharge prevention electrolyte for lithium ion batteries |
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|---|---|
| CN102780041A true CN102780041A (en) | 2012-11-14 |
Family
ID=47124869
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|---|---|---|---|
| CN2012102659870A Pending CN102780041A (en) | 2012-07-30 | 2012-07-30 | Overcharge prevention electrolyte for lithium ion batteries |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106025344A (en) * | 2016-07-01 | 2016-10-12 | 东风商用车有限公司 | Lithium ion battery flame-retardant electrolyte |
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| CN101685880A (en) * | 2008-09-25 | 2010-03-31 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of electrolyte of low-temperature lithium ion battery |
| CN101904101A (en) * | 2007-12-19 | 2010-12-01 | 松下电器产业株式会社 | Encoder, decoder, encoding method, and decoding method |
-
2012
- 2012-07-30 CN CN2012102659870A patent/CN102780041A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101000970A (en) * | 2006-01-11 | 2007-07-18 | 比亚迪股份有限公司 | Electrolyte and lithium ion battery containing the electrolyte and preparation method thereof |
| CN101904101A (en) * | 2007-12-19 | 2010-12-01 | 松下电器产业株式会社 | Encoder, decoder, encoding method, and decoding method |
| CN101308939A (en) * | 2008-01-31 | 2008-11-19 | 东莞市杉杉电池材料有限公司 | Electrolyte of over charge preventing lithium ionic cell |
| CN101299471A (en) * | 2008-06-10 | 2008-11-05 | 深圳市雷天电源技术有限公司 | Composite electrolytic solution of lithium ion power battery and preparation method thereof |
| CN101685880A (en) * | 2008-09-25 | 2010-03-31 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of electrolyte of low-temperature lithium ion battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106025344A (en) * | 2016-07-01 | 2016-10-12 | 东风商用车有限公司 | Lithium ion battery flame-retardant electrolyte |
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Application publication date: 20121114 |