CN102769148A - High-power lithium ion battery electrolyte - Google Patents
High-power lithium ion battery electrolyte Download PDFInfo
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- CN102769148A CN102769148A CN201210205620XA CN201210205620A CN102769148A CN 102769148 A CN102769148 A CN 102769148A CN 201210205620X A CN201210205620X A CN 201210205620XA CN 201210205620 A CN201210205620 A CN 201210205620A CN 102769148 A CN102769148 A CN 102769148A
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Abstract
The invention discloses a high-power lithium ion battery electrolyte. A technical scheme provided by the invention has the following main points: the high-power lithium ion battery electrolyte comprises an electrolyte salt, a non-aqueous organic solvent and an additive; the electrolyte salt is selected from the group consisting of lithium hexafluorophosphate with lithium bis(oxalate)borate, lithium difluoroborate and a mixture thereof; the non-aqueous organic solvent is a mixture of ethylene carbonate, dimethyl carbonate and propylene carbonate; and the additive is a mixture of perfluorinated glycol sulfite derivative, ethylene carbonate and cyclic carboxylic ester-butyrolactone. The high-power lithium ion battery electrolyte can well support a high-power power battery for charging and discharging with large current; the lithium ion battery prepared by using the electrolyte has excellent rate capability and cycle performance, and can effectively prevent inflation of a battery using a ternary high nickel material.
Description
Technical field
The present invention relates to technical field of lithium ion, be specifically related to a kind of electrolyte of high power lithium ion battery prepared.
Background technology
In the last few years, the energy in the whole world, resource were day by day nervous, and problem of environmental pollution also becomes increasingly conspicuous, and each state is all greatly developing the new forms of energy industry.Current, it also is the inexorable trend of social development that electric automobile replaces fuel-engined vehicle gradually, therefore efficient, the convenient hot subject that has become current society research with the novel energy of safety non-pollution of research and development.Lithium ion battery is as a kind of novel secondary cell; Because it has high-energy-density and power density, memory-less effect, operating voltage height, good cycle, load capacity is strong, security performance good and plurality of advantages such as non-environmental-pollution, much has a wide range of applications in fields in mancarried electronic aid, electronic traffic electrical source of power, electric tool, large-scale energy storage, military and space etc.
Electrolyte of lithium-ion secondary battery is the important component part of lithium rechargeable battery, is bearing the charge transfer between the both positive and negative polarity, and it plays crucial effects to capacity, high rate performance, cycle efficieny, operating temperature range and the security performance of battery.Electrolyte of lithium-ion secondary battery generally comprises electrolytic salt, high-purity non-aqueous organic solvent and additive.Electrolytic salt is concerning the ionic conductivity of lithium secondary cell electrolyte and the formation of electrode passivation film.Organic solvent and additive constitute the solvent of lithium secondary battery, are generally mixed by base solvent with high dielectric constant and more low viscous organic solvent, add necessary additive again and form.
The solvent that contains in most of lithium-ion battery electrolytes in the market can not form stable solid electrolyte phase boundary facial mask well; Lithium ion along with solvation in the battery use is embedded into graphite layers together; On the graphite electrode material surface decomposition taking place graphite linings is peeled off, causes the high rate performance variation and the cycle performance of lithium ion battery to descend gradually then.The problems referred to above cause lithium ion battery not to be applied in well in the electrokinetic cell field.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that overcomes prior art; Provide a kind of and can support well that the high power electrokinetic cell carries out the electrolyte of high power lithium ion battery prepared of high current charge-discharge; Use the lithium ion battery of this electrolyte preparation to have excellent high rate performance and cycle performance, and can effectively prevent to use the battery generation inflatable of ternary high-nickel material.
The technical scheme that adopts of the present invention is: a kind of electrolyte of high power lithium ion battery prepared; Comprise electrolytic salt, non-aqueous organic solvent and additive; It is characterized in that: described electrolytic salt is made up of A and B; Wherein A is a lithium hexafluoro phosphate, and B is diacetic acid lithium borate, difluorine oxalic acid boracic acid lithium or their mixture; Described non-aqueous organic solvent is the mixture of ethylene carbonate, dimethyl carbonate and propene carbonate; Described additive is the mixture of ethylene sulfite derivative, ethylene carbonate and the cyclic carboxylic esters-butyrolactone of perfluoro.
Electrolyte of high power lithium ion battery prepared of the present invention; It is characterized in that: the composition quality percentage composition of described electrolytic salt is respectively: lithium hexafluoro phosphate accounts for 60% ~ 90%, and the mixture of diacetic acid lithium borate or difluorine oxalic acid boracic acid lithium or diacetic acid lithium borate and difluorine oxalic acid boracic acid lithium accounts for 10% ~ 40%.
Electrolyte of high power lithium ion battery prepared of the present invention is characterized in that: the composition quality percentage composition of described non-aqueous organic solvent is respectively: ethylene carbonate accounts for 30% ~ 60%, and dimethyl carbonate accounts for 10% ~ 20%, and propene carbonate accounts for 20% ~ 60%.
Electrolyte of high power lithium ion battery prepared of the present invention; It is characterized in that: the composition quality percentage composition of described additive is respectively: the ethylene sulfite derivative of perfluoro accounts for 40% ~ 60%; Ethylene carbonate accounts for 15% ~ 25%, and cyclic carboxylic esters-butyrolactone accounts for 15% ~ 45%.
Wherein, the structural formula of the ethylene sulfite derivative of perfluoro is following:
In the said structure formula, R
1And R
2Be respectively carbon number and be 1 ~ 10 perfluoro carbochain.
Electrolyte of high power lithium ion battery prepared of the present invention is characterized in that: the oeverall quality with non-aqueous organic solvent and additive is 100% calculating, and each component in the said electrolyte and mass fraction thereof are distinguished as follows:
Organic solvent: 50% ~ 96%
Additive: 4% ~ 50%
The molar concentration of electrolytic salt in electrolyte is 0.6 ~ 1.4 mol/L.
Electrolyte of high power lithium ion battery prepared of the present invention, it is characterized in that preferred electrolyte consists of: electrolytic salt is lithium hexafluoro phosphate and difluorine oxalic acid boracic acid lithium; Non-aqueous organic solvent is the mixture of ethylene carbonate, dimethyl carbonate and propene carbonate; Additive is the mixture of ethylene sulfite derivative, ethylene carbonate and the cyclic carboxylic esters-butyrolactone of perfluoro.Preferably the oeverall quality with non-aqueous organic solvent and additive is 100% calculating, and wherein each component and mass percent thereof are following:
Ethylene carbonate: 25%
Dimethyl carbonate: 18%
Propene carbonate: 35%
The ethylene sulfite derivative of perfluoro: 11%
Ethylene carbonate: 3%
Cyclic carboxylic esters-butyrolactone: 8%
Electrolytic salt is lithium hexafluoro phosphate and difluorine oxalic acid boracic acid lithium, and mass fraction is respectively 60% and 40%, and the molar concentration in electrolyte is 1 mol/L.
A kind of lithium rechargeable battery that uses electrolyte of high power lithium ion battery prepared preparation of the present invention; It is characterized in that: said battery possesses positive electrode, negative electrode and barrier film; Positive electrode, negative electrode and barrier film all are immersed in the described electrolyte subsequent use, and described electrolyte of high power lithium ion battery prepared can be used to prepare high power lithium ion cell.
Beneficial effect of the present invention is following:
1. the invention provides a kind of high-power lithium ion electrolyte; Its reasonable mixture ratio of components; Graphite electrode surface at lithium secondary battery can form stable, the fine and close solid electrolyte phase boundary facial mask of one deck; Therefore the common imbedding problem that can effectively stop the lithium ion of organic solvent and solvation can improve capacity, high rate performance and the cycle efficieny of the lithium secondary battery that uses electrolyte of the present invention greatly;
2. electrolytic salt lithium hexafluoro phosphate facile hydrolysis also can decompose generation HF in the water of trace.HF can destroy the solid electrolyte phase boundary facial mask on graphite material surface, is prone to make battery to produce ballooning, increases the irreversible capacity loss of battery, reduces the cycle efficieny of battery.But difluorine oxalic acid boracic acid lithium and diacetic acid lithium borate are insensitive to water, can not generate HF because of the existence of water, and it can form stable fine and close solid electrolyte phase boundary facial mask in negative terminal surface, and it has excellent cycle performance and security performance in addition.So the present invention adopts lithium hexafluoro phosphate to mix use with difluorine oxalic acid boracic acid lithium or diacetic acid lithium borate;
The present invention adopt ethylene carbonate with high conductance as base solvent with mix than the low viscosity solvent dimethyl carbonate; When it has high conductance in assurance; Still can keep proper viscosity, add high-melting-point solvent propene carbonate in addition and can support better that the high power electrokinetic cell carries out high current charge-discharge.Battery is when carrying out multiplying power discharging; Battery temperature raises very fast; Be prone to make battery generation ballooning; For fear of inflatable, in electrolyte of the present invention, added the additive ethylene carbonate with anti-inflatable function, the ethylene sulfite derivative and the cyclic carboxylic esters-butyrolactone of perfluoro, can prevent battery generation inflatable effectively;
4. the high power electrolyte that lithium rechargeable battery provided by the invention uses can support well that electrokinetic cell carries out high current charge-discharge; Use the lithium ion battery of this electrolyte of high power lithium ion battery prepared preparation to have excellent high rate performance and cycle performance, and can effectively prevent to use the battery generation inflatable of ternary high-nickel material.
Description of drawings
Fig. 1 is for pressing the high rate performance curve chart of embodiment 1 prepared sample;
Fig. 2 is for pressing the cyclic curve figure of embodiment 1 and Comparative Examples 1 prepared sample.
Embodiment
For fully understanding content of the present invention and characteristics, further specify through specific embodiment and Comparative Examples below:
What be used to test in following embodiment and the Comparative Examples all is 18650 batteries.
Described 18650 batteries obtain through following method assembling:
With LiNi
1/3Co
1/3Mn
1/3O
2, acetylene black, PVDF mixes according to 91: 4: 3 mass ratio; Add an amount of NMP (N-N-methyl-2-2-pyrrolidone N-) solvent and become uniform slurry; Two-sidedly evenly be coated on the aluminium foil; After removing moisture and solvent, then in the twin rollers compacting, cutting obtains the positive plate of certain width and thickness again.With graphite carbon black, acetylene black, SBR (butadiene-styrene rubber) and CMC (sodium carboxymethylcellulose) according to 92: 2: 3.50: 2.50 mass ratio mixes; Adding suitable quantity of water mixes; Reach viscosity 5000～6000 cps and be advisable, two-sided evenly being coated on the Copper Foil, remove moisture and solvent after; In the twin rollers compacting, cutting obtains the negative plate of certain width and thickness more then.Make through pole piece baking, lug then and operation such as coiling, add electrolyte of the present invention and seal at glove box.At last battery is changed into and electric performance test.
Embodiment 1
Electrolyte is formed as follows: the oeverall quality with organic solvent and additive is 100% calculating; Non-aqueous organic solvent wherein: the mass fraction of ethylene carbonate, dimethyl carbonate, propene carbonate is respectively: 25%, 18%, 35%; The ethylene sulfite derivative of additive perfluoro, ethylene carbonate, cyclic carboxylic esters-butyrolactone mass fraction are respectively: 11%, 3%, 8%; Electrolytic salt is lithium hexafluoro phosphate and difluorine oxalic acid boracic acid lithium; Mass fraction is respectively 60% and 40%, and the molar concentration in electrolyte is 1 mol/L.Add this electrolyte and process the electrical property of this battery of 18650 battery testings under 1 C, 5 C, 10 C and 15 C multiplying powers, it is respectively 1456 mAh, 1404 mAh, 1447 mAh and 1473 mAh by capacity, sees Fig. 1; Wherein under the 10 C multiplying powers, capacity is 1398 mAh after 400 circulations, and capability retention is 96%, sees Fig. 2.
Embodiment 2
Electrolyte is formed as follows: the oeverall quality with organic solvent and additive is 100% calculating; Non-aqueous organic solvent wherein: the mass fraction of ethylene carbonate, dimethyl carbonate, propene carbonate is respectively: 28%, 16%, 34%; The mass fraction of the ethylene sulfite derivative of additive perfluoro, ethylene carbonate, cyclic carboxylic esters-butyrolactone is respectively 9%, 6%, 7%; Electrolytic salt is lithium hexafluoro phosphate and diacetic acid lithium borate; Mass fraction is respectively 70% and 30%; Molar concentration in electrolyte is 1 mol/L, adds this electrolyte and processes the electrical property of this battery of 18650 battery testings under 1 C, 5 C, 10 C and 15 C multiplying powers, and it is respectively 1463 mAh, 1402 mAh, 1441 mAh and 1469 mAh by capacity; Wherein under the 10 C multiplying powers, 400 circulation volumes remain on 1396 mAh, and capability retention is 95%.
Embodiment 3
Electrolyte is formed as follows: the oeverall quality with organic solvent and additive is 100% calculating; Non-aqueous organic solvent wherein: the mass fraction of ethylene carbonate, dimethyl carbonate, propene carbonate is respectively: 15%, 5%, 30%; The mass fraction of the ethylene sulfite derivative of additive perfluoro, ethylene carbonate, cyclic carboxylic esters-butyrolactone is respectively 20%, 7.5%, 22.5%; Electrolytic salt is the mixture of lithium hexafluoro phosphate and difluorine oxalic acid boracic acid lithium and diacetic acid lithium borate; Mass fraction is respectively 90%, 5%, 5%; Molar concentration in electrolyte is 0.6mol/L, adds this electrolyte and processes the electrical property of this battery of 18650 battery testings under 1 C, 5 C, 10 C and 15 C multiplying powers, and it is respectively 1430 mAh, 1371 mAh, 1350 mAh and 1326 mAh by capacity; Wherein under the 10 C multiplying powers, 400 circulation volumes remain on 1293 mAh, and capability retention is 90%.
Embodiment 4
Electrolyte is formed as follows: the oeverall quality with organic solvent and additive is 100% calculating; Non-aqueous organic solvent wherein: the mass fraction of ethylene carbonate, dimethyl carbonate, propene carbonate is respectively: 57%, 19%, 19%; The mass fraction of the ethylene sulfite derivative of additive perfluoro, ethylene carbonate, cyclic carboxylic esters-butyrolactone is respectively 2%, 0.75%, 2.25%; Electrolytic salt is the mixture of lithium hexafluoro phosphate and difluorine oxalic acid boracic acid lithium and diacetic acid lithium borate; Mass fraction is respectively 60%, 20%, 20%; Molar concentration in electrolyte is 1.4 mol/L, adds this electrolyte and processes the electrical property of this battery of 18650 battery testings under 1 C, 5 C, 10 C and 15 C multiplying powers, and it is respectively 1472 mAh, 1400 mAh, 1456 mAh and 1479 mAh by capacity; Wherein under the 10 C multiplying powers, 400 circulation volumes remain on 1412 mAh, and capability retention is 96%.
Comparative Examples 1
Electrolyte is formed as follows: the oeverall quality with organic solvent and additive is 100% calculating; Non-aqueous organic solvent wherein: the mass fraction of ethylene carbonate, dimethyl carbonate, propene carbonate is respectively: 36%, 17%, 39%; The mass fraction of additive ethylene carbonate is divided into 8%; Electrolytic salt is lithium hexafluoro phosphate and difluorine oxalic acid boracic acid lithium, and mass fraction is respectively 60% and 40%, and the molar concentration in electrolyte is 1 mol/L.Add this electrolyte and process the electrical property of this battery of 18650 battery testings under 1 C, 5 C, 10 C and 15 C multiplying powers, it is respectively 1113 mAh, 1102 mAh, 1141 mAh and 1169 mAh by capacity; Wherein under the 10 C multiplying powers, 400 circulation volumes remain on 880 mAh, and capability retention is 77%, sees Fig. 2.
Claims (8)
1. electrolyte of high power lithium ion battery prepared; Comprise electrolytic salt, non-aqueous organic solvent and additive; It is characterized in that: said electrolytic salt is made up of A and B, and wherein A is a lithium hexafluoro phosphate, and B is diacetic acid lithium borate, difluorine oxalic acid boracic acid lithium or their mixture; Described non-aqueous organic solvent is the mixture of ethylene carbonate, dimethyl carbonate and propene carbonate; Described additive is the mixture of ethylene sulfite derivative, ethylene carbonate and the cyclic carboxylic esters-butyrolactone of perfluoro.
2. electrolyte of high power lithium ion battery prepared according to claim 1; It is characterized in that: the composition quality percentage composition of described electrolytic salt is respectively: lithium hexafluoro phosphate accounts for 60% ~ 90%, and the mixture of diacetic acid lithium borate or difluorine oxalic acid boracic acid lithium or diacetic acid lithium borate and difluorine oxalic acid boracic acid lithium accounts for 10% ~ 40%.
3. electrolyte of high power lithium ion battery prepared according to claim 1; It is characterized in that: the composition quality percentage composition of described non-aqueous organic solvent is respectively: ethylene carbonate accounts for 30% ~ 60%; Dimethyl carbonate accounts for 10% ~ 20%, and propene carbonate accounts for 20% ~ 60%.
4. electrolyte of high power lithium ion battery prepared according to claim 1; It is characterized in that: the composition quality percentage composition of described additive is respectively: the ethylene sulfite derivative of perfluoro accounts for 40% ~ 60%; Ethylene carbonate accounts for 15% ~ 25%, and cyclic carboxylic esters-butyrolactone accounts for 15% ~ 45%.
Wherein, the structural formula of the ethylene sulfite derivative of perfluoro is following:
In the said structure formula, R
1And R
2Be respectively carbon number and be 1 ~ 10 perfluoro carbochain.
5. electrolyte of high power lithium ion battery prepared according to claim 1 is characterized in that: the oeverall quality with non-aqueous organic solvent and additive is 100% calculating, and each component in the described electrolyte of high power lithium ion battery prepared and mass fraction thereof are distinguished as follows:
Organic solvent: 50% ~ 96%
Additive: 4% ~ 50%
The molar concentration of electrolytic salt in electrolyte is 0.6 ~ 1.4 mol/L.
6. according to claim 1 or 5 described electrolyte of high power lithium ion battery prepared, it is characterized in that electrolyte consists of: electrolytic salt is lithium hexafluoro phosphate and difluorine oxalic acid boracic acid lithium; Non-aqueous organic solvent is the mixture in ethylene carbonate, dimethyl carbonate and the propene carbonate; Additive is the mixture of ethylene sulfite derivative, ethylene carbonate and the cyclic carboxylic esters-butyrolactone of perfluoro.Oeverall quality with non-aqueous organic solvent and additive is 100% calculating, and each component and mass percent thereof are following in the described electrolyte of high power lithium ion battery prepared:
Ethylene carbonate: 25%
Dimethyl carbonate: 18%
Propene carbonate: 35%
The ethylene sulfite derivative of perfluoro: 11%
Ethylene carbonate: 3%
Cyclic carboxylic esters-butyrolactone: 8%
Electrolytic salt is lithium hexafluoro phosphate and difluorine oxalic acid boracic acid lithium, and mass fraction is respectively 60% and 40%, and the molar concentration in electrolyte is 1 mol/L.
7. one kind is used the lithium rechargeable battery that each described electrolyte of high power lithium ion battery prepared prepares in the claim 1 ~ 5; It is characterized in that: said battery possesses positive electrode, negative electrode and barrier film, and positive electrode, negative electrode and barrier film all are immersed in the described electrolyte of high power lithium ion battery prepared subsequent use.
8. a lithium rechargeable battery that uses each described electrolyte of high power lithium ion battery prepared preparation in the claim 1 ~ 5 is characterized in that: the application of described electrolyte of high power lithium ion battery prepared in the preparation high power lithium ion cell.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022555A (en) * | 2012-12-30 | 2013-04-03 | 无锡富洪科技有限公司 | Lithium ion battery and preparation method thereof |
| CN108680701A (en) * | 2018-04-04 | 2018-10-19 | 珠海市赛纬电子材料股份有限公司 | The detection method of the inorganic salt compound of class containing oxalic acid in a kind of lithium hexafluorophosphate electrolyte solution |
| CN111200163A (en) * | 2020-01-09 | 2020-05-26 | 荣盛盟固利新能源科技有限公司 | EC-free lithium ion battery electrolyte suitable for high nickel-silicon-carbon system |
| CN113707943A (en) * | 2021-08-25 | 2021-11-26 | 中国科学院长春应用化学研究所 | Electrolyte and double-ion battery |
| CN114006039A (en) * | 2021-09-29 | 2022-02-01 | 林丰川 | Long-cycle-life graphene-rare metal compatible battery and electrolyte thereof |
| CN117976991A (en) * | 2024-03-27 | 2024-05-03 | 宁德新能源科技有限公司 | Nonaqueous electrolyte, lithium ion battery and electronic device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101304101A (en) * | 2008-07-09 | 2008-11-12 | 东莞市杉杉电池材料有限公司 | Cylinder type lithium ion battery electrolytic solution and preparation method thereof |
| CN102208683A (en) * | 2011-05-16 | 2011-10-05 | 湖州创亚动力电池材料有限公司 | Electrolyte for improving high-temperature storage performance of lithium-ion secondary battery |
-
2012
- 2012-06-21 CN CN201210205620XA patent/CN102769148A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101304101A (en) * | 2008-07-09 | 2008-11-12 | 东莞市杉杉电池材料有限公司 | Cylinder type lithium ion battery electrolytic solution and preparation method thereof |
| CN102208683A (en) * | 2011-05-16 | 2011-10-05 | 湖州创亚动力电池材料有限公司 | Electrolyte for improving high-temperature storage performance of lithium-ion secondary battery |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022555A (en) * | 2012-12-30 | 2013-04-03 | 无锡富洪科技有限公司 | Lithium ion battery and preparation method thereof |
| CN108680701A (en) * | 2018-04-04 | 2018-10-19 | 珠海市赛纬电子材料股份有限公司 | The detection method of the inorganic salt compound of class containing oxalic acid in a kind of lithium hexafluorophosphate electrolyte solution |
| CN111200163A (en) * | 2020-01-09 | 2020-05-26 | 荣盛盟固利新能源科技有限公司 | EC-free lithium ion battery electrolyte suitable for high nickel-silicon-carbon system |
| CN113707943A (en) * | 2021-08-25 | 2021-11-26 | 中国科学院长春应用化学研究所 | Electrolyte and double-ion battery |
| CN114006039A (en) * | 2021-09-29 | 2022-02-01 | 林丰川 | Long-cycle-life graphene-rare metal compatible battery and electrolyte thereof |
| CN117976991A (en) * | 2024-03-27 | 2024-05-03 | 宁德新能源科技有限公司 | Nonaqueous electrolyte, lithium ion battery and electronic device |
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Application publication date: 20121107 |