CN107579279A - A kind of lithium-ion electrolyte for improving lithium ion pole piece interface - Google Patents
A kind of lithium-ion electrolyte for improving lithium ion pole piece interface Download PDFInfo
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- CN107579279A CN107579279A CN201710715471.4A CN201710715471A CN107579279A CN 107579279 A CN107579279 A CN 107579279A CN 201710715471 A CN201710715471 A CN 201710715471A CN 107579279 A CN107579279 A CN 107579279A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention provides a kind of lithium-ion electrolyte for improving lithium ion pole piece interface, is related to technical field of lithium ion.The lithium-ion electrolyte that the present invention improves lithium ion pole piece interface is made up of organic solvent, lithium salts, additive, wherein, the percentage that each component accounts for lithium-ion battery electrolytes gross mass is respectively：Lithium salts 15% 27%, additive 1.5% 6%, surplus is organic solvent.The present invention improves the lithium-ion electrolyte at lithium ion pole piece interface, improve the heat endurance for the SEI films that lithium battery is formed in first charge-discharge, extend lithium battery charge and discharge cycles service life at low temperature, the probability that lithium battery produces tympanites reduces, so as to improve the security performance of lithium battery and chemical property, the potential safety hazard of lithium ion battery is reduced.
Description
Technical field
The present invention relates to technical field of lithium ion, is related to a kind of lithium ion electrolysis for improving lithium ion pole piece interface
Liquid.
Background technology
Lithium ion battery is due to the features such as operating voltage is high, energy density is high, have extended cycle life, environmentally friendly, extensively
Applied to fields such as 3C digital products, electric automobile, military aerospaces.As the improvement of people's living standards, to lithium ion battery
Working environment, energy density, fast charging and discharging propose higher requirement.Lithium ion battery at low ambient temperatures its discharge energy
Power decay is very fast, and low temperature environment charging cathode interface easily analyses lithium, and so as to make the irreversible damage of battery pair, situation is tight
More likely because battery analysis lithium produces potential safety hazard during weight.And a kind of mode for lifting battery energy density is to improve battery pole piece
Compacted density, but the raising of compacted density mean material mass transfer conduction speed reduce, impedance increase, cause battery to make
During easily there is phenomena such as analysis lithium, blackspot in pole piece.On the other hand, because positive pole exists during lithium battery quick charge
Deviate from more lithium ions in unit interval and enter negative pole, under the driving of high current often due to the reason for negative pole mass transfer impedance
So that lithium ion can not be completely embedded into inside negative pole, cause to analyse lithium, blocking lithium ion transport passage so as to rest on outside pole piece,
In the course of time battery is thickening, deforms, and easily causes security risk.
Therefore, battery during Reusability cathode pole piece interface quality to the specific function of battery, service life,
There is considerable influence in terms of security, need badly and develop the electrolyte that can improve cathode pole piece interface to meet battery to low temperature charge and discharge
Electricity, fast charging and discharging, the demand of comprehensive electrochemical properties under high compacted density system.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of lithium-ion electrolyte for improving lithium ion pole piece interface.
To realize object above, the present invention is achieved by the following technical programs：
A kind of lithium-ion electrolyte for improving lithium ion pole piece interface, the lithium-ion electric for improving lithium ion pole piece interface
Solution liquid is made up of organic solvent, lithium salts, additive, wherein, each component accounts for the percentage score of lithium-ion battery electrolytes gross mass
It is not：Lithium salts 15%-27%, additive 1.5%-6%, surplus are organic solvent；The lithium salts is complexing lithium borate, complexing phosphorus
At least one of sour lithium, lithium perchlorate, hexafluoro lithium borate, three (trimethyl fluoride sulfonyl) lithium methides；The organic solvent is by ring
Shape carbonic ether, diethyl carbonate, ether compound composition.Wherein, lithium borate, complexing lithium phosphate, lithium perchlorate, hexafluoro boron are complexed
Sour lithium, three (trimethyl fluoride sulfonyl) lithium methides, the type lithium salts is by controlling anion to introduce other electron-withdrawing groups in the molecule
Group, so as to control the chemical stability of lithium salts and electrochemical stability, and the lithium salts is soluble in organic solvent and dissociation, ensures
The electric conductivity of electrolyte.
Further, the organic solvent is mixed by the raw material of following percentage by weight：Cyclic carbonate fat 25-
55%th, diethyl carbonate 20-50%, ether compound 20-35%.
Further, the purity of the cyclic carbonate fat is 99.95%, and the purity of the diethyl carbonate is 99.67%,
The purity of the ether compound is 98.92%.
Further, the ether compound is dioxolane, 1.2- dimethoxy-ethanes, glycol dimethyl ether, diethyl
At least one of glycol dimethyl ether, 2- methyltetrahydrofurans.
Further, the cyclic carbonate fat be two bistrichloromethyl carbonates, fluorinated ethylene carbonate, ethylene carbonate,
At least one of ethyl methyl carbonate；Cyclic carbonate fat stable performance, it is not susceptible to decompose in graphite electrode surface, coordinates
Additive is easily forming stable SEI films on graphite cathode surface, avoids and reduces the phenomenon that charging analysis lithium occurs, have excellent
Different high temperature performance and anti-inflatable performance, effectively lift battery capacity and cycle performance.
Further, the additive include into gas film additive, Isosorbide-5-Nitrae-butane sultones, vinylene carbonate,
At least one of fluorinated ethylene carbonate.
Further, the gas film for additive is one kind in carbon dioxide, sulfur dioxide, carbon monoxide；Dioxy
It is main SEI film film for additive to change carbon, sulfur dioxide, carbon monoxide, and these gases can promote the shape of stable SEI films
Into the molecular film on electrode top layer is stable, reduces the common insertion of solvent molecule, and then prevent the peeling of graphite electrode so that electrolysis
Cathode interface of the liquid under low temperature, fast charging and discharging environment is good, avoids and reduce the phenomenon that charging analysis lithium occurs.
Further, the additive also includes functional additive.
Further, the functional additive is one kind in methyl phenyl ethers anisole, ethylene sulfite, dimethyl sulfite；
Methyl phenyl ethers anisole is added in lithium-ion battery electrolytes, the cycle performance of battery can be improved, reduces the irreversible capacity damage of battery
Lose, the discharge platform of battery can be extended so that battery has good electric conductivity and cycle performance, improves the charge and discharge of battery
Electrical property.
The present invention provides a kind of lithium-ion electrolyte for improving lithium ion pole piece interface, and advantage exists compared with prior art
In：
The present invention improves the lithium-ion electrolyte at lithium ion pole piece interface, improves what lithium battery was formed in first charge-discharge
The heat endurance of SEI films, extends lithium battery charge and discharge cycles service life at low temperature, and the probability that lithium battery produces tympanites subtracts
It is small, so as to improve the security performance of lithium battery and chemical property, reduce the potential safety hazard of lithium ion battery；
The present invention improves lithium-ion electrolyte being used in combination by each component at lithium ion pole piece interface so that electrolyte
Cathode interface under low temperature, fast charging and discharging environment is good, the phenomenon that charging analysis lithium occurs is avoided and reduce, so as to same
When meet low temperature discharge and recharge, fast charging and discharging, cathode pole piece high compacted density battery system demand, and reduce battery analysis
Lithium and caused potential safety hazard；
The present invention improves in the lithium-ion electrolyte raw material at lithium ion pole piece interface, and lithium salts is from complexing lithium borate, complexing
Lithium phosphate, lithium perchlorate, hexafluoro lithium borate, three (trimethyl fluoride sulfonyl) lithium methides, the type lithium salts is by controlling anion to exist
Other electron withdraw groups are introduced in molecule, so as to control the chemical stability of lithium salts and electrochemical stability, and the lithium salts is easy
Organic solvent and dissociation are dissolved in, ensures the electric conductivity of electrolyte；Organic solvent is by cyclic carbonate fat, diethyl carbonate, ethers
Compound group is into wherein cyclic carbonate fat stable performance is not susceptible to decompose in graphite electrode surface, coordinates additive in stone
Black negative terminal surface easily forms stable SEI films, has excellent high temperature performance and anti-inflatable performance, effectively lifts battery and holds
Amount and cycle performance；
Gas film for additive carbon dioxide, sulfur dioxide, carbon monoxide in the electrolytic solution is main SEI film film forming
Additive, these gases can promote the formation of stable SEI films, and the molecular film on electrode top layer is stable, reduces being total to for solvent molecule
It is embedded, and then prevent the peeling of graphite electrode so that cathode interface of the electrolyte under low temperature, fast charging and discharging environment is good,
Avoid and reduce the phenomenon that charging analysis lithium occurs；The reduction of vinylene carbonate, fluorinated ethylene carbonate and functional additive
Current potential is high, can be preferentially reduced on Carbon anode, so as to preferably suppress capacity attenuation in cyclic process.In lithium ion battery battery
Methyl phenyl ethers anisole is added in solution liquid, the cycle performance of battery can be improved, reduce the irreversible capacity loss of battery, battery can be extended
Discharge platform so that battery has good electric conductivity and cycle performance, improves the charge-discharge performance of battery.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, with reference to embodiment to the present invention
Technical scheme in embodiment is clearly and completely described, it is clear that described embodiment is that a part of the invention is implemented
Example, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making creativeness
The every other embodiment obtained under the premise of work, belongs to the scope of protection of the invention.
Embodiment 1：
In the present embodiment, preparing for the lithium-ion electrolyte at improvement lithium ion pole piece interface is as follows：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, organic solvent is configured, is by purity
98.92% 2 bistrichloromethyl carbonate 25%, purity are 99.67% diethyl carbonate 50%, purity is 98.92% ethers chemical combination
Thing 1.2- dimethoxy-ethanes 25% mix, and stir, obtain organic solvent, take and account for lithium-ion battery electrolytes gross mass
The lithium that the percentage for being slowly added to account for lithium-ion battery electrolytes gross mass in the organic solvent that percentage is 83.5% is 15%
Salt be complexed lithium borate, be slow added into account for lithium-ion battery electrolytes gross mass percentage be 1.5% additive Isosorbide-5-Nitrae-fourth
Sultone, stir under carbon dioxide atmosphere and be completely dissolved to it, obtain the lithium-ion electrolyte of embodiment 1.
Embodiment 2：
In the present embodiment, preparing for the lithium-ion electrolyte at improvement lithium ion pole piece interface is as follows：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, organic solvent is configured, is by purity
98.92% fluorinated ethylene carbonate 55%, purity are 99.67% diethyl carbonate 20%, purity is 98.92% ether compound
Dioxolane 25% mixes, and stirs, obtains organic solvent, takes the percentage for accounting for lithium-ion battery electrolytes gross mass to be
The percentage for being slowly added to account for lithium-ion battery electrolytes gross mass in 67% organic solvent is 27% lithium perchlorate, then delays
The vinylene carbonate that the percentage that slow addition accounts for lithium-ion battery electrolytes gross mass is 6%, stirs to it and is completely dissolved, obtain
To the lithium-ion electrolyte of embodiment 2.
Embodiment 3：
In the present embodiment, preparing for the lithium-ion electrolyte at improvement lithium ion pole piece interface is as follows：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, organic solvent is configured, is by purity
98.92% cyclic carbonate fat 45%, purity are 99.67% diethyl carbonate 30%, purity is 98.92% ether compound 25%
Mixing, stir, obtain organic solvent, (wherein, cyclic carbonate fat be two bistrichloromethyl carbonates, fluorinated ethylene carbonate,
Ethylene carbonate, ethyl methyl carbonate are by weight 1:1:1:1 mixes, and ether compound is dioxolane, 1.2- bis-
Ethyl Methyl Ether, glycol dimethyl ether are by weight 1:1:1 mixes), take and account for the hundred of lithium-ion battery electrolytes gross mass
The lithium salts that the percentage for dividing ratio to be slowly added to account for lithium-ion battery electrolytes gross mass in 75% organic solvent is 20%, then
The additive that the percentage for being slowly added to account for lithium-ion battery electrolytes gross mass is 5%, under carbon dioxide atmosphere, stirring is extremely
It is completely dissolved, and obtains the lithium-ion electrolyte of embodiment 3.
Wherein lithium salts is complexing lithium borate, is complexed lithium phosphate, lithium perchlorate, hexafluoro lithium borate by weight 2:2:1:1 is mixed
Conjunction forms；Additive is vinylene carbonate, fluorinated ethylene carbonate, methyl phenyl ethers anisole by weight 2:1:2 mix.
Embodiment 4：
In the present embodiment, preparing for the lithium-ion electrolyte at improvement lithium ion pole piece interface is as follows：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, organic solvent is configured, by ethyl-methyl
Carbonic ester 50%, diethyl carbonate 30%, 2- methyltetrahydrofurans 20% mix, and stir, obtain organic solvent, take and account for lithium
The percentage of ion battery electrolyte gross mass is to be slowly added to account for the total matter of lithium-ion battery electrolytes in 72% organic solvent
The percentage of amount be 25% lithium salts, be slow added into account for lithium-ion battery electrolytes gross mass percentage be 3% addition
Agent, under carbon monoxide atmosphere, stir to it and be completely dissolved, obtain the lithium-ion electrolyte of embodiment 4.
Wherein lithium salts is complexing lithium borate, is complexed lithium phosphate, lithium perchlorate, hexafluoro lithium borate, three (trimethyl fluoride sulfonyls)
Lithium methide is according to weight than 2:2:0.5:1:0.3；Additive is Isosorbide-5-Nitrae-butane sultones, vinylene carbonate, fluoro carbonic acid
Vinyl acetate, ethylene sulfite are according to weight than 1.3:2:0.6:0.3.
Embodiment 5：
In the present embodiment, preparing for the lithium-ion electrolyte at improvement lithium ion pole piece interface is as follows：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, organic solvent is configured, by cyclic carbonate
Fat 35%, diethyl carbonate 30%, ether compound 35% mix, and stir, obtain organic solvent, take and account for lithium ion battery
The percentage of electrolyte gross mass is the percentage for being slowly added to account for lithium-ion battery electrolytes gross mass in 74% organic solvent
Than the lithium salts for 20%, the additive for accounting for that the percentage of lithium-ion battery electrolytes gross mass is 6% is slow added into, in dioxy
Change under sulphur atmosphere, stir to it and be completely dissolved, obtain the lithium-ion electrolyte of embodiment 5.
Wherein, cyclic carbonate fat is two bistrichloromethyl carbonates, fluorinated ethylene carbonate, ethylene carbonate, ethyl-methyl
Carbonic ester mixes；Ether compound is dioxolane, 1.2- dimethoxy-ethanes, glycol dimethyl ether, diethylene glycol two
Methyl ether, 2- methyltetrahydrofurans mix；Lithium salts for complexing lithium borate, complexing lithium phosphate, lithium perchlorate, hexafluoro lithium borate,
Three (trimethyl fluoride sulfonyl) lithium methides mix；Additive is Isosorbide-5-Nitrae-butane sultones, vinylene carbonate, fluoro carbonic acid
Vinyl acetate, dimethyl sulfite mix.
Comparative example 1：
In this comparative example, the preparation of lithium-ion battery electrolytes：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, organic solvent is configured, by carbonic acid diethyl
Ester 50%, ethylene carbonate 50% mixes, and stirs, obtains organic solvent, takes and accounts for lithium-ion battery electrolytes gross mass
Double fluorine that the percentage for being slowly added to account for lithium-ion battery electrolytes gross mass in the organic solvent that percentage is 55% is 20%
Sulfimide lithium, the percentage for accounting for lithium-ion battery electrolytes gross mass is 20% diethyl diethylene glycol diethyl ether, is slow added into and accounts for
The percentage of lithium-ion battery electrolytes gross mass is 5% ethylene sulfite, stirs to it and is completely dissolved, obtains comparative example
1 lithium-ion battery electrolytes.
Comparative example 2：
In this comparative example, the preparation of lithium-ion battery electrolytes：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, organic solvent is configured, by carbonic acid diethyl
Ester 50%, methyl ethyl carbonate 50% mixes, and stirs, obtains organic solvent, takes and accounts for lithium-ion battery electrolytes gross mass
Double fluorine that the percentage for being slowly added to account for lithium-ion battery electrolytes gross mass in the organic solvent that percentage is 55% is 20%
Sulfimide lithium, the percentage for accounting for lithium-ion battery electrolytes gross mass is 20% diethyl diethylene glycol diethyl ether, is slow added into and accounts for
The percentage of lithium-ion battery electrolytes gross mass is 5% tetraethyl ammonium tetrafluoroborate, stirs to it and is completely dissolved, and is obtained pair
The lithium-ion battery electrolytes of ratio 2.
Lithium-ion battery electrolytes prepared by the embodiment 1-5 electrolyte prepared and comparative example 1-2, are injected separately into positive pole
Active matter cobalt acid lithium LiCoO2, in negative electrode active material LA-1 soft bag lithium ionic cell, battery after fluid injection is encapsulated, shelve,
The work steps such as chemical conversion, aging, secondary encapsulation, partial volume, obtain lithium ion battery to be tested.Each battery is subjected to performance test again,
Test result is as shown in Tables 1 and 2.
The different lithium ion battery the performance test results of table 1
As shown in the data of table 1, the battery capacity prepared by 1-5 of embodiment of the present invention electrolyte is higher than comparative example, Er Qieben
Battery prepared by invention electrolyte does not analyse lithium, and 45 DEG C of circulation volume conservation rates are high, and electrolyte self-extinguishing time is short, the battery tool of preparation
There are good electric conductivity, cycle performance, charge-discharge performance etc..
The different lithium ion battery performance cycle capacity attenuation test results of table 2
Lithium-ion electric can be obviously improved by the electrolyte that it can be seen from -20 DEG C of loop-around datas prepared by the present invention of table 2
The cycle performance of pond under cryogenic, electrolyte show that electrolyte prepared by the present invention can be with bright in 55 DEG C of loop-around data results
The high temperature cyclic performance of aobvious lifting lithium ion battery.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
The present invention is described in detail, it will be understood by those within the art that：It still can be to foregoing each implementation
Technical scheme described in example is modified, or carries out equivalent substitution to which part technical characteristic；And these modification or
Replace, the essence of appropriate technical solution is departed from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (9)
- A kind of 1. lithium-ion electrolyte for improving lithium ion pole piece interface, it is characterised in that the improvement lithium ion pole piece interface Lithium-ion electrolyte be made up of organic solvent, lithium salts, additive, wherein, each component accounts for lithium-ion battery electrolytes gross mass Percentage be respectively：Lithium salts 15%-27%, additive 1.5%-6%, surplus are organic solvent；The lithium salts is complexing boron At least one of sour lithium, complexing lithium phosphate, lithium perchlorate, hexafluoro lithium borate, three (trimethyl fluoride sulfonyl) lithium methides；It is described to have Solvent is made up of cyclic carbonate fat, diethyl carbonate, ether compound.
- 2. the lithium-ion electrolyte according to claim 1 for improving lithium ion pole piece interface, it is characterised in that described organic Solvent is mixed by the raw material of following percentage by weight：Cyclic carbonate fat 25-55%, diethyl carbonate 20-50%, ethers Compound 20-35%.
- 3. the lithium-ion electrolyte according to claim 1 or 2 for improving lithium ion pole piece interface, it is characterised in that：It is described The purity of cyclic carbonate fat is 99.95%, and the purity of the diethyl carbonate is 99.67%, the purity of the ether compound For 98.92%.
- 4. the lithium-ion electrolyte for improving lithium ion pole piece interface according to claim 1 or 2 or 3, it is characterised in that：Institute Ether compound is stated as dioxolane, 1.2- dimethoxy-ethanes, glycol dimethyl ether, diethylene glycol dimethyl ether, 2- methyl four At least one of hydrogen furans.
- 5. the lithium-ion electrolyte for improving lithium ion pole piece interface according to claim 1 or 2 or 3, it is characterised in that：Institute State cyclic carbonate fat for two bistrichloromethyl carbonates, fluorinated ethylene carbonate, ethylene carbonate, in ethyl methyl carbonate extremely Few one kind.
- 6. the lithium-ion electrolyte according to claim 1 for improving lithium ion pole piece interface, it is characterised in that：The addition Agent is included at least one in gas film additive, Isosorbide-5-Nitrae-butane sultones, vinylene carbonate, fluorinated ethylene carbonate Kind.
- 7. the lithium-ion electrolyte according to claim 6 for improving lithium ion pole piece interface, it is characterised in that：The gas Film for additive is one kind in carbon dioxide, sulfur dioxide, carbon monoxide.
- 8. the lithium-ion electrolyte according to claim 6 for improving lithium ion pole piece interface, it is characterised in that：The addition Agent also includes functional additive.
- 9. the lithium-ion electrolyte according to claim 8 for improving lithium ion pole piece interface, it is characterised in that：The function Additive is one kind in methyl phenyl ethers anisole, ethylene sulfite, dimethyl sulfite.
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| CN108376800A (en) * | 2018-02-02 | 2018-08-07 | 江苏海基新能源股份有限公司 | The electrolyte and lithium ion battery of high-temperature lithium ion battery cycle performance can be improved |
| CN108847502A (en) * | 2018-05-08 | 2018-11-20 | 东风商用车有限公司 | High-low temperature electrolyte for lithium iron phosphate battery |
| CN112054242A (en) * | 2020-08-04 | 2020-12-08 | 昆山宝创新能源科技有限公司 | Electrolyte and application thereof |
| CN112310473A (en) * | 2019-07-30 | 2021-02-02 | 东莞市杉杉电池材料有限公司 | High-low temperature lithium ion battery electrolyte and lithium ion battery |
| CN112886060A (en) * | 2021-01-12 | 2021-06-01 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device, and electronic device |
| US20220045362A1 (en) * | 2019-04-26 | 2022-02-10 | Contemporary Amperex Technology Co., Limited | Electrolyte, lithium-ion battery, and apparatus containing such lithium-ion battery |
| CN114597496A (en) * | 2022-03-24 | 2022-06-07 | 湖北亿纬动力有限公司 | Electrolyte and lithium ion battery containing same |
| CN116259846A (en) * | 2023-04-11 | 2023-06-13 | 湖北亿纬动力有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| WO2024011611A1 (en) * | 2022-07-15 | 2024-01-18 | 宁德时代新能源科技股份有限公司 | Nonaqueous electrolyte, secondary battery, and electrical device |
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