CN106785038A - A kind of siliceous electrolyte of lithium ion battery - Google Patents
A kind of siliceous electrolyte of lithium ion battery Download PDFInfo
- Publication number
- CN106785038A CN106785038A CN201611224394.4A CN201611224394A CN106785038A CN 106785038 A CN106785038 A CN 106785038A CN 201611224394 A CN201611224394 A CN 201611224394A CN 106785038 A CN106785038 A CN 106785038A
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- China
- Prior art keywords
- additive
- electrolyte
- battery
- ion battery
- siliceous
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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 present invention relates to a kind of siliceous electrolyte of lithium ion battery, belong to the technical field of lithium-ion battery electrolytes, including lithium salts, organic solvent and additive, lithium salts concentration in organic solvent is 1 1.5mol/L, the consumption of additive is 0.5% 10%, described organic solvent is 0.2 1.2 containing siloxane solvent and carbonate-based solvent including mass ratio, it is carbonic acid two (trimethyl silicon substrate) ester wherein containing siloxane solvent, described additive includes occupying mass percent for 0.2 2% film for additive, 0.5 3% anti-overcharge additive and 0.1 2% positive pole protection additive.The present invention passes through reasonable preparation additive so that the electrolysis liquid energy containing such additives effectively improves the charge-discharge performance of lithium battery, reduces the generation of side reaction, so as to reduce battery flatulence, improves battery cycle life.
Description
Technical field
The invention belongs to the technical field of lithium battery electrolytes, it is related to a kind of siliceous electrolyte of lithium ion battery.
Background technology
Lithium ion battery has the advantages that operating voltage is high, energy density is high because of it, environment-friendly, stable circulation, safe,
It is widely used in the various electronic equipments of notebook computer, mobile phone, MP4 etc..But with battery capacity in electronic equipment
Improve, people it is also proposed requirement higher to the operating voltage and energy density of lithium ion battery.
Electrolyte is the important component of battery, carries and ion is transmitted between positive and negative electrode by inside battery
Effect, its capacity to battery, operating temperature range, cycle performance and security performance etc. have important influence.Electrolyte is general
It is divided into liquid electrolyte and the class of solid electrolyte two, following basic demand need to be met：(1) ionic conductivity high, should typically reach
To 1 × 10-3-2×10-2S/cm；(2) heat endurance and chemical stability high, do not occur point within the scope of temperature wider
Solution；(3) electrochemical window wider, keeps the stabilization of chemical property in voltage range wider；(4) with other portions of battery
Dividing has good compatibility；(5) it is safe and nontoxic, pollution-free.
Liquid organic solution liquid is the most commonly used, but as the range of application of battery is constantly widened, people are to battery
The requirement of each side is continuously increased, and original electrolyte system can not meet use requirement.Add in the electrolytic solution a small amount of
Cucumber, some performances of battery, such as electrical conductivity of electrolyte, the cycle efficieny of battery and reversible appearance can be significantly improved
Amount, security performance of battery etc., these a small amount of materials are referred to as functional additive.Generally require and add in the electrolytic solution some work(
Can property additive realize some specific functions of battery, functional additive is in the production and research of battery using increasingly
It is many.
Safety is primary to battery all the time in use, and it is an important index to overcharge, typically except in electricity
Set by perimeter security in the assembling process of pond and improved outside safety with protection circuit plate, also from battery design and the electrolyte of battery
Etc. aspect improved.Realize that overcharging for battery is protected for simplifying battery manufacturing process and reduction using electrolysis additive
Cost has very important significance, and can typically consider from the following aspects：1st, redox shuttle, 2, flame-retardant electrolyte,
3rd, self closing additive agent electrolyte.
Anti-overcharge additive is added in electrolyte can effectively improve the security of battery, but additive is not more
It is better, as long as being not to overcharge qualified it is ensured that other projects are similarly outstanding.The addition of anti-overcharge additive excessively can
Other performances of battery are influenceed, such as battery capacity reduction, circulation is deteriorated, and safety test bulging is exceeded etc..Therefore, general additive
Use to be reduced as far as possible in the case where effect is reached, and in order to obtain good effect, the list that different additive has
One using effect is good, and what is had then needs compound use more preferably, and the species and addition of additive need to be carefully studied.Additionally, being
The influence that the addition of additive is caused to battery other performance is reduced, be improved in the form of being combined using various ways and overcharged
The usage amount of additive is reduced while performance.
The content of the invention
The present invention devises a kind of siliceous electrolyte of lithium ion battery, by reasonable preparation to solve the above problems
Additive so that the electrolysis liquid energy containing such additives effectively improves the charge-discharge performance of lithium battery, reduces side reaction
Occur, so as to reduce battery flatulence, improve battery cycle life.
The present invention is to realize that the technical scheme that its purpose is used is：
A kind of siliceous electrolyte of lithium ion battery, including lithium salts, organic solvent and additive, lithium salts is in organic solvent
Concentration be 1-1.5mol/L, the consumption of additive is 0.5%-10%, and key point is, described organic solvent include quality it
Than being 0.2-1.2 containing siloxane solvent and carbonate-based solvent, wherein be carbonic acid two (trimethyl silicon substrate) ester containing siloxane solvent, it is described
Additive includes occupying mass percent for 0.2-2% film for additive, the anti-overcharge additives of 0.5-3% and 0.1-2% positive poles
Protection additive.
Described carbonic ester is cyclic carbonate, and the ratio between cyclic carbonate and volume of carbonic acid two (trimethyl silicon substrate) ester are
1:1.15-4。
Described cyclic carbonate be selected from ethylene carbonate, propene carbonate, gamma-butyrolacton in one or more
Combination.
Described film for additive is selected from cyclopentene triketone, vinylene carbonate, vinyl ethylene carbonate, 1,3- propane
One or more combination in sultones, 1,3- propene sultones, 1,4- butane sultones.
Described anti-overcharge additive is selected from biphenyl, cyclohexyl benzene, 2- fluorine biphenyl, 2,4- DfBPs, 2,3,4- trifluoros
One or more combination in biphenyl.
Described positive pole protection additive is selected from HMDS, hexaethyl disilazine, six propyl group disilazanes
In one or more combination.
Described lithium salts is selected from LiPF6、LiBF4、LiSO3F3、LiClO4、Li(CF3SO2)N2、Li(CF3SO2)3In one kind
Or two or more combinations.
The beneficial effects of the invention are as follows：The present invention passes through reasonable preparation additive so that the electrolysis containing such additives
Liquid energy effectively improves the charge-discharge performance of lithium battery, reduces the generation of side reaction, so as to reduce battery flatulence, improves battery and follows
The ring life-span.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated.
First, specific embodiment
Embodiment 1
Organic solvent is ethylene carbonate, (both volume ratios are 40 to carbonic acid two (trimethyl silicon substrate) ester:60)；Lithium salts is
LiPF6, lithium salt is 1M/L, and film for additive is ethylene carbonate, and accounting is 2%, and anti-overcharge additive is 2,4- difluoros
Biphenyl, accounting is 1%, and positive pole protection additive is HMDS, and accounting is 0.2%.
Embodiment 2
Organic solvent is ethylene carbonate, (both volume ratios are 30 to carbonic acid two (trimethyl silicon substrate) ester:70)；Lithium salts is
LiPF6, lithium salt is 1M/L, and film for additive is ethylene carbonate and 1,3- propene sultone, and accounting is respectively 1%, is prevented
Overcharging additive is 2,4- DfBPs, and accounting is 1%, and positive pole protection additive is HMDS, and accounting is
0.2%.
Embodiment 3
Organic solvent is ethylene carbonate, (both volume ratios are 30 to carbonic acid two (trimethyl silicon substrate) ester:70)；Lithium salts is
LiPF6, lithium salt is 1M/L, and film for additive is ethylene carbonate and 1,3- propane sultone, and accounting is respectively 1%, is prevented
Overcharging additive is 2- fluorine biphenyl, and accounting is 1%, and positive pole protection additive is HMDS, and accounting is 0.2%.
Embodiment 4
Organic solvent is ethylene carbonate, (both volume ratios are 30 to carbonic acid two (trimethyl silicon substrate) ester:70)；Lithium salts is
LiPF6, lithium salt is 1M/L, and film for additive is ethylene carbonate and 1,3- propane sultone, and accounting is respectively 1%, is prevented
Overcharging additive is 2- fluorine biphenyl, and accounting is 2%, and positive pole protection additive is HMDS, and accounting is 0.2%.
Embodiment 5
Organic solvent is ethylene carbonate, (both volume ratios are 30 to carbonic acid two (trimethyl silicon substrate) ester:70)；Lithium salts is
LiPF6, lithium salt is 1M/L, and film for additive is ethylene carbonate and Isosorbide-5-Nitrae-butane sultones, and accounting is respectively 1%, is prevented
Overcharging additive is 2- fluorine biphenyl, and accounting is 2%, and positive pole protection additive is HMDS, and accounting is 0.2%.
Comparative example
Electrolyte, it includes organic solvent, lithium salts and additive, and the organic solvent is having in addition to containing siloxane solvent
Machine solvent.
2nd, performance test
Cycle performance test will be carried out after the electrolyte of electrolyte of the invention and comparative example respectively assembled battery, method is such as
Under：With cobalt acid lithium as positive electrode, negative pole uses carbonaceous mesophase spherules, both positive and negative polarity collector to be distributed as aluminium foil and Copper Foil, barrier film
Soft-package battery is constituted using ceramic diaphragm, after injection electrolyte, soft-package battery is assembled into glove box, stand 8 hours it is laggard
Row test.Discharge and recharge is carried out under 25 DEG C of constant temperature of room temperature with 1/10C 3.0V to 4.2V respectively to activate battery, then exist
Circulation under the conditions of 45 DEG C is with 1C discharge and recharges.Loop test the results are shown in Table 1.
Table 1
Battery discharge conservation rate under different multiplying：By battery with 0.5C constant-current discharges to 3.0V, shelve 5min, then with
0.5C constant-current charges are 0.05C by electric current to 4.4V, and constant-voltage charge, stand 5min, then respectively with 0.2C, 1C, 1.5C,
2C constant-current discharges are to by voltage 3.0V.Discharge capacity under the conditions of record 0.2C, 1C, 1.5C, 2C is D1, under record 0.2C
Discharge capacity is D0, and based on the discharge capacity under 0.2C, by discharge capacitance=[(the D1-D0)/D0] of battery ×
100% formula is calculated discharge capacitance (survey 15 batteries, take its average value) of the battery under different multiplying, respectively
Individual battery is in 25 DEG C of conditions, and the discharge capacitance under different multiplying is as shown in table 2.
Table 2
Battery high-temperature storge quality is evaluated：60 DEG C/7D and 85 DEG C/7D storage performances are tested, and following table 3 is that battery handles mark
60 DEG C of storages are deposited 7 days for 7 days and 85 DEG C again after quasi- discharge and recharge, then the capability retention and capacity restoration rate of measurement battery.
Table 3
Battery low-temperature storage performance evaluation；Table 4 below is that battery is shelved in cryogenic box, and it is -30 DEG C that temperature is controlled respectively
Or -40 DEG C, time 240min is shelved, then the capability retention of measurement battery.
Table 4
Hot tank is tested：Battery carries out following tests：
1) battery is charged to by 4.4V with the constant current of 1.0C electric currents, then constant-voltage charge to electric current is down to 0.05C, charging stops
Only；2) battery is placed in hot tank, is started to warm up to 180 DEG C from 25 DEG C with the programming rate of 5 DEG C/min, tieed up after reaching 180 DEG C
Hold temperature-resistant, then start timing, the state of battery is observed after 1h, the standard by the test is：Without smoldering, nothing rises battery
Fire, without blast, wherein every group of 5 batteries.The result of the hot tank test of each battery is as shown in table 5.Tested by above-mentioned hot tank,
Characterize the security performance of battery.
Table 5
| Project | State after hot tank test |
| Embodiment 1 | 5 batteries pass through, and do not smolder, on fire, explosion phenomenon |
| Embodiment 2 | 5 batteries pass through, and do not smolder, on fire, explosion phenomenon |
| Embodiment 3 | 5 batteries pass through, and do not smolder, on fire, explosion phenomenon |
| Embodiment 4 | 5 batteries pass through, and do not smolder, on fire, explosion phenomenon |
| Embodiment 5 | 5 batteries pass through, and do not smolder, on fire, explosion phenomenon |
| Comparative example | 2 batteries pass through, and 2 batteries are smoldered, 1 battery catches fire |
Claims (7)
1. the siliceous electrolyte of a kind of lithium ion battery, including lithium salts, organic solvent and additive, lithium salts is in organic solvent
Concentration is 1-1.5mol/L, and the consumption of additive is 0.5%-10%, it is characterised in that described organic solvent include quality it
Than being 0.2-1.2 containing siloxane solvent and carbonate-based solvent, wherein be carbonic acid two (trimethyl silicon substrate) ester containing siloxane solvent, it is described
Additive includes occupying mass percent for 0.2-2% film for additive, the anti-overcharge additives of 0.5-3% and 0.1-2% positive poles
Protection additive.
2. the siliceous electrolyte of a kind of lithium ion battery according to claim 1, it is characterised in that：Described carbonic ester is
The ratio between volume of cyclic carbonate, cyclic carbonate and carbonic acid two (trimethyl silicon substrate) ester is 1:1.15-4.
3. the siliceous electrolyte of a kind of lithium ion battery according to claim 2, it is characterised in that：Described cyclic carbonate
Ester is selected from one or more the combination in ethylene carbonate, propene carbonate, gamma-butyrolacton.
4. the siliceous electrolyte of a kind of lithium ion battery according to claim 1, it is characterised in that：Described film forming addition
Agent is selected from vinylene carbonate, vinyl ethylene carbonate, 1,3- propane sultones, 1,3- propene sultones, 1,4- fourths
One or more combination in sultone.
5. the siliceous electrolyte of a kind of lithium ion battery according to claim 1, it is characterised in that：It is described anti-overcharge to add
Plus agent be selected from biphenyl, cyclohexyl benzene, 2- fluorine biphenyl, 2,4- DfBPs, 2,3,4- trifluoro-biphenyls in one or more
Combination.
6. the siliceous electrolyte of a kind of lithium ion battery according to claim 1, it is characterised in that：Described positive pole protection
Additive is selected from one or more the group in HMDS, hexaethyl disilazine, six propyl group disilazanes
Close.
7. the siliceous electrolyte of a kind of lithium ion battery according to claim 1, it is characterised in that：Described lithium salts is selected from
LiPF6、LiBF4、LiSO3F3、LiClO4、Li(CF3SO2)N2、Li(CF3SO2)3In one or more combination.
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| CN201611224394.4A CN106785038A (en) | 2016-12-27 | 2016-12-27 | A kind of siliceous electrolyte of lithium ion battery |
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| CN201611224394.4A CN106785038A (en) | 2016-12-27 | 2016-12-27 | A kind of siliceous electrolyte of lithium ion battery |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107910591A (en) * | 2017-11-14 | 2018-04-13 | 石家庄圣泰化工有限公司 | A kind of high-temperature-reslithium lithium battery electrolyte |
| CN109244529A (en) * | 2018-09-13 | 2019-01-18 | 杉杉新材料（衢州）有限公司 | A kind of lithium ion battery high-voltage electrolyte and the lithium ion battery using the electrolyte |
| CN109346771A (en) * | 2018-09-21 | 2019-02-15 | 杉杉新材料（衢州）有限公司 | A kind of lithium ion battery high-voltage electrolyte and lithium ion battery |
| CN109786830A (en) * | 2018-12-24 | 2019-05-21 | 杉杉新材料（衢州）有限公司 | A kind of electrolyte containing siloxane solvent and thiophene-based additive and the lithium ion battery using the electrolyte |
| CN109786831A (en) * | 2018-12-25 | 2019-05-21 | 杉杉新材料（衢州）有限公司 | A kind of electrolyte containing siloxane solvent and pyrazoles additive and the lithium ion battery using the electrolyte |
| CN109802178A (en) * | 2018-12-26 | 2019-05-24 | 杉杉新材料（衢州）有限公司 | A kind of electrolyte containing siloxane solvent and sulfonic acid esters additive and the lithium ion battery using the electrolyte |
| CN109802177A (en) * | 2018-12-25 | 2019-05-24 | 杉杉新材料（衢州）有限公司 | A kind of electrolyte containing siloxane solvent and pyridined additives and the lithium ion battery using the electrolyte |
| WO2020151647A1 (en) * | 2019-01-25 | 2020-07-30 | Ningde Amperex Technology Limited | Electrolyte solution and electrochemical device using the same |
| CN111883838A (en) * | 2020-08-03 | 2020-11-03 | 香河昆仑化学制品有限公司 | Non-aqueous electrolyte and lithium ion battery |
| CN112652818A (en) * | 2021-01-12 | 2021-04-13 | 东莞维科电池有限公司 | Electrolyte for lithium ion battery and lithium ion battery |
| CN113140794A (en) * | 2021-03-30 | 2021-07-20 | 山东海容电源材料股份有限公司 | Electrolyte film forming additive and lithium ion battery electrolyte containing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107910591A (en) * | 2017-11-14 | 2018-04-13 | 石家庄圣泰化工有限公司 | A kind of high-temperature-reslithium lithium battery electrolyte |
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| CN109244529A (en) * | 2018-09-13 | 2019-01-18 | 杉杉新材料（衢州）有限公司 | A kind of lithium ion battery high-voltage electrolyte and the lithium ion battery using the electrolyte |
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| CN109786830A (en) * | 2018-12-24 | 2019-05-21 | 杉杉新材料（衢州）有限公司 | A kind of electrolyte containing siloxane solvent and thiophene-based additive and the lithium ion battery using the electrolyte |
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| CN109786831A (en) * | 2018-12-25 | 2019-05-21 | 杉杉新材料（衢州）有限公司 | A kind of electrolyte containing siloxane solvent and pyrazoles additive and the lithium ion battery using the electrolyte |
| CN109802177B (en) * | 2018-12-25 | 2020-10-16 | 杉杉新材料（衢州）有限公司 | Electrolyte containing silicon solvent and pyridine additive and lithium ion battery using electrolyte |
| CN109802178A (en) * | 2018-12-26 | 2019-05-24 | 杉杉新材料（衢州）有限公司 | A kind of electrolyte containing siloxane solvent and sulfonic acid esters additive and the lithium ion battery using the electrolyte |
| WO2020151647A1 (en) * | 2019-01-25 | 2020-07-30 | Ningde Amperex Technology Limited | Electrolyte solution and electrochemical device using the same |
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| CN111883838A (en) * | 2020-08-03 | 2020-11-03 | 香河昆仑化学制品有限公司 | Non-aqueous electrolyte and lithium ion battery |
| CN111883838B (en) * | 2020-08-03 | 2023-05-12 | 香河昆仑新能源材料股份有限公司 | Nonaqueous electrolyte and lithium ion battery |
| CN112652818A (en) * | 2021-01-12 | 2021-04-13 | 东莞维科电池有限公司 | Electrolyte for lithium ion battery and lithium ion battery |
| CN113140794A (en) * | 2021-03-30 | 2021-07-20 | 山东海容电源材料股份有限公司 | Electrolyte film forming additive and lithium ion battery electrolyte containing same |
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