CN106159321A - A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery - Google Patents
A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery Download PDFInfo
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- CN106159321A CN106159321A CN201510148518.4A CN201510148518A CN106159321A CN 106159321 A CN106159321 A CN 106159321A CN 201510148518 A CN201510148518 A CN 201510148518A CN 106159321 A CN106159321 A CN 106159321A
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- 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
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- 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
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Abstract
The invention provides a kind of non-aqueous electrolyte for lithium ion cell and a kind of lithium ion battery, described nonaqueous electrolytic solution includes lithium salts, organic solvent and additive, it is characterised in that described additive has a structure shown in formula (1):
Description
Technical field
The invention belongs to field of lithium ion battery, particularly relate to a kind of non-aqueous electrolyte for lithium ion cell and the lithium ion battery containing this nonaqueous electrolytic solution.
Background technology
Lithium ion battery so that its high voltage, high power capacity, low consumption, memory-less effect, nuisanceless and volume be little etc., show one's talent from numerous battery varieties by advantage, is widely used in mobile phone, listens at any time, in numerous electronic product such as PDA, Notebook.
Prior art discloses a kind of electrolyte for lithium cells with silica-base material as negative material and lithium ion battery, this electrolyte includes: lithium salts, non-aqueous organic solvent, film for additive, wherein, described non-aqueous organic solvent includes ethylene carbonate, described film for additive includes three (pentafluorophenyl group) borine (TPFPB), content is described electrolyte gross weight the 1%～7% of described three (pentafluorophenyl group) borine.Adding TPFPB main purpose is to be formed on negative material surface to stablize complete SEI film, weaken the powder phenomenon-tion that silica-base material causes as the bulk effect of silicon during negative material, and TPFPB can discharge the lithium ion moved freely by SEI film, thus can balance out the part lithium ion consumed in the forming process of SEI film, reduce lithium ion consumption, thus improve efficiency for charge-discharge and cycle performance, but addition the most just can play such effect, sees patent CN103413969A；Simultaneously, three (pentafluorophenyl group) borine (TPFPB) this kind of fluorine-containing material has the disadvantage in that three (pentafluorophenyl group) borine (TPFPB) addition does not has the effect above very little, and add too much, it can easily be reduced generation fluohydric acid gas (HF) around silicium cathode, HF reacts generation LiF further with electrolyte, LiF is enriched with at silicium cathode as solid, negative pole SEI film is caused constantly to thicken, hinder lithium ion transmission between electrolyte and negative pole, battery charging and discharging performance reduces, battery impedance increases, gas produces the most notable simultaneously, cell expansion is bigger, cycle performance of battery is caused to deteriorate；Additionally, TPFPB easily decomposes when using (such as more than 60 DEG C) in the environment of temperature is higher, the fluoro-gas produced is the most easily and silicium cathode generation side reaction, cause the avalanche of silicon material structure and the peeling of electrode material, so that electrode material loses activity, the cycle performance of silicon cathode lithium ion battery is caused drastically to decline.
Summary of the invention
The present invention solves the problem that lithium ion battery efficiency for charge-discharge in prior art is low and the life-span is short, and particularly evident for the efficiency for charge-discharge of silicon cathode lithium ion battery and the raising of cycle performance.
The present invention provides a kind of non-aqueous electrolyte for lithium ion cell, including lithium salts, organic solvent and additive, it is characterised in that described additive has a structure shown in formula (1):
Wherein, R be carbon number be the alkyl of 1-4.
Present invention also offers a kind of lithium ion battery, including housing and the battery core being contained in housing, nonaqueous electrolytic solution, battery core includes positive pole, negative pole and the barrier film between positive pole and negative pole, described positive pole includes positive electrode active materials, conductive agent and binding agent, described negative pole includes negative active core-shell material and binding agent, described negative active core-shell material is nano silicon material, wherein, and the nonaqueous electrolytic solution that described nonaqueous electrolytic solution provides for the present invention.
The nonaqueous electrolytic solution that the present invention provides, it is possible to solve the problem that in prior art, lithium ion battery efficiency for charge-discharge is low and the life-span is short.
Especially when the nonaqueous electrolytic solution that the present invention provides is in silicon cathode lithium ion battery, the additive provided due to the present invention comprises sulfate group and trialkylsilanyl group, the common effect rolled into a ball by sulfate group and trialkylsilanyl can improve the compatibility between electrolyte and silicium cathode material, additive can form stable SEI film when formation charging on silicium cathode surface simultaneously, can alleviate, reaction between suppression Li-Si alloy and organic solvent, silicium cathode is played a good protection, thus it is effectively improved the charge-discharge performance of silicon cathode lithium ion battery, reduce the generation of side reaction and reduce silicium cathode volumetric expansion, improve the cycle life of silicon cathode lithium ion battery.As a example by double (TMS) sulfuric esters that R obtains for methyl, during Battery formation charging, double (TMS) sulfuric ester occurs reductive polymerization to react on negative pole, forms cyclic sulfates or wire sulfuric ester, and course of reaction is shown in as follows:
Or
And cyclic sulfates or wire sulfuric ester are the main components having resilient SEI film; the SEI film produced can be alleviated, suppress the reaction between Li-Si alloy and organic solvent; silicium cathode is played a good protection; thus it is effectively improved the charge-discharge performance of silicon cathode lithium ion battery; reduce the generation of side reaction and reduce silicium cathode volumetric expansion, improving the cycle life of silicon cathode lithium ion battery.
Detailed description of the invention
The invention provides a kind of non-aqueous electrolyte for lithium ion cell, including lithium salts, organic solvent and additive, it is characterised in that described additive has a structure shown in formula (1):
Wherein, R is the alkyl of carbon number 1-4.
It was found by the inventors of the present invention that by adding a small amount of additive of the present invention in non-aqueous electrolyte for lithium ion cell, lithium ion battery cycle performance under room temperature and hot conditions can be made significantly to promote.The structure of this additive is, is respectively symmetrically, at the two ends, left and right of sulfate group, the hydrogen atom connected on a silylation, and the silane group at two ends and is all replaced by the alkyl that identical carbon number is 1-4.This additive can improve the problem that lithium ion battery efficiency for charge-discharge in prior art is low and the life-span is short.Particularly with silicon cathode lithium ion battery, owing to this additive comprises sulfate group and trialkylsilanyl group simultaneously, the common effect of sulfate group and trialkylsilanyl group can improve the compatibility between electrolyte and silicium cathode material, and this additive can form stable SEI film when lithium ion battery formation charging on silicium cathode surface, can alleviate, reaction between suppression Li-Si alloy and organic solvent, the charge-discharge performance of silicon cathode lithium ion battery can be effectively improved, reduce the generation of side reaction and reduce silicium cathode volumetric expansion, thus improve the cycle life of silicon cathode lithium ion battery.
In formula (1), R is methyl, ethyl, propyl group, butyl, described additive can selected from therein one or more.Under preferable case, R is methyl or ethyl.
When R is methyl, obtaining described additive is double (TMS) sulfuric esters, shown in its structural formula such as formula (2):
When R is ethyl, obtaining described additive is double (triethyl silyl) sulfuric esters, shown in its structural formula such as formula (3):
Described additive can also be double (TMS) sulfuric ester and the mixing of double (triethyl silyl) sulfuric ester, and the weight ratio between the most double (TMS) sulfuric esters and double (triethyl silyl) sulfuric ester can arbitrarily select.
In non-aqueous electrolyte for lithium ion cell of the present invention, on the basis of the gross weight of nonaqueous electrolytic solution, the content of additive is preferably 0.1-2wt%, during the too high levels of this additive, the SEI film formed at cathode interface can be made blocked up, causing cathode impedance to become big, the cycle performance ultimately resulting in battery reduces；And if content is too low, the effect of good cycle performance of lithium ion battery can not be reached again.It is further preferred that on the basis of the gross weight of non-aqueous electrolyte for lithium ion cell, the content of described additive is 0.5-1.5wt%.
In non-aqueous electrolyte for lithium ion cell of the present invention, described nonaqueous solvent uses the various nonaqueous solvents that those skilled in the art commonly use, such as, can be selected from least one in carboxylic acid esters solvent, carbonate-based solvent, nitrile solvents or ketones solvent.Under preferable case, described nonaqueous solvent is selected from one or more of ethylene carbonate (EC), Allyl carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl methyl carbonate (EMC), methyl formate (MF), methyl acetate (MA), methyl propionate (MP), ethyl acetate (EP), adiponitrile (ADN) or succinonitrile (SN).Optionally, described nonaqueous solvent is selected from the mixing of any two kinds of solvents in ethylene carbonate (EC), Allyl carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl methyl carbonate (EMC), methyl formate (MF), methyl acetate (MA), methyl propionate (MP), ethyl acetate (EP), adiponitrile (ADN) or succinonitrile (SN), and the weight ratio of two kinds of solvents is preferably 1:0.5-3；Described nonaqueous solvent can also be selected from the mixing of any three kinds of solvents in ethylene carbonate (EC), Allyl carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl methyl carbonate (EMC), methyl formate (MF), methyl acetate (MA), methyl propionate (MP), ethyl acetate (EP), adiponitrile (ADN) or succinonitrile (SN), and the weight ratio of three kinds of solvents is preferably 1:0.3-1.0:0.5-1.5；Described nonaqueous solvent is also selected from the mixing of any four solvent in ethylene carbonate (EC), Allyl carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl methyl carbonate (EMC), methyl formate (MF), methyl acetate (MA), methyl propionate (MP), ethyl acetate (EP), adiponitrile (ADN) or succinonitrile (SN), and the weight ratio of four kinds of solvents is preferably 1:1-1.6:0.2-1.3:0.1-0.8.Preferably, the mixing of the described nonaqueous solvent any two or three solvent in ethylene carbonate (EC), Allyl carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl methyl carbonate (EMC), methyl formate (MF), methyl acetate (MA), methyl propionate (MP), ethyl acetate (EP), adiponitrile (ADN) or succinonitrile (SN).
In non-aqueous electrolyte for lithium ion cell of the present invention, described lithium salts is the various lithium salts that those skilled in the art commonly use, such as, can be selected from lithium hexafluoro phosphate (LiPF6), lithium chlorate (LiClO4), LiBF4 (LiBF4), hexafluoroarsenate lithium (LiAsF6), hexafluorosilicic acid lithium (LiSiF6), tetrachloro-lithium aluminate (LiAlCl4), double second dioxalic acid Lithium biborate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI), trifluoromethayl sulfonic acid lithium (LiCF3SO3), double (trifluoroacetyl group) inferior amine salt (Li (CF3CO2)2N), double (trimethyl fluoride sulfonyl) imine lithium (Li (CF3SO2)2Or double (pentafluoroethyl group sulphonyl) imine lithium (Li (SO N)2C2F5)2N) one or more in, the concentration of lithium salts is the concentration that this area is conventional, and with weight percentage, the weight of lithium salts is the 8.5-18.5wt% of described electrolyte gross weight, and under preferable case, the present invention uses LiPF6As lithium salts, its concentration is 8.5-18.5wt%, preferably 10-16wt%.
The preparation method of the non-aqueous electrolyte for lithium ion cell that the present invention provides, common method for those skilled in the art, will each component (including lithium salts, nonaqueous solvent and additive) mix homogeneously, to mixing mode and order the present invention be all not particularly limited.
Present invention also offers a kind of lithium ion battery, including housing and the battery core being contained in housing, nonaqueous electrolytic solution, battery core includes positive pole, negative pole and the barrier film between positive pole and negative pole, described positive pole includes positive electrode active materials, conductive agent and binding agent, described negative pole includes negative active core-shell material and binding agent, described negative active core-shell material is nano silicon material, it is characterised in that the nonaqueous electrolytic solution that described nonaqueous electrolytic solution provides for the present invention.Further, the nano silicon material that negative pole is used is preferably silicon nanowire material or the silicon nanowire material of carbon cladding.It is prepared as silicium cathode battery by the silicon nanowire material using silicon nanowire material or carbon cladding; silicium cathode battery uses the non-aqueous electrolyte for lithium ion cell that the present invention provides; stable SEI film can be formed on silicium cathode surface; can alleviate, suppress the reaction between Li-Si alloy and organic solvent; silicium cathode is played a good protection; thus it is effectively improved the charge-discharge performance of silicon cathode lithium ion battery; reduce the generation of side reaction and reduce silicium cathode volumetric expansion, improving the cycle life of silicium cathode battery.Wherein silicon nanowire material is the silicon nanowire material that this area is conventional, such as particle diameter can be selected from 10-500nm, draw ratio (L/D ratio) can be selected from the tubular nanometer silicon materials of 10-100, under preferable case, the present invention uses particle diameter to be 50-200nm, draw ratio is the silicon nanowire material of 20-60.It addition, the technology that the preparation technology of the positive plate of lithium ion battery, negative plate, barrier film is well known in the art, and the technology that the assembling of battery is the most well known in the art, just repeat no more at this.
Below in conjunction with embodiment, the non-aqueous electrolyte for lithium ion cell of the present invention and the lithium ion battery containing this nonaqueous electrolytic solution are described further.
Embodiment 1
(1) preparation of nonaqueous electrolytic solution:
Vinyl carbonate (EC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC) are mixed as nonaqueous solvent, by the lithium hexafluoro phosphate (LiPF of 13 weight portions by weight the ratio of 2:1:36) be dissolved in the nonaqueous solvent of 86 weight portions, it is subsequently adding double (TMS) sulfuric esters (compound as shown in formula (2)) of 1 weight portion, obtains the non-aqueous electrolyte for lithium ion cell of the present embodiment, be designated as C1；
(2) preparation of lithium ion battery:
LiCoO2 (cobalt acid lithium), PVDF (Kynoar), CNT (CNT) with on aluminium foil, are obtained positive plate by compacting after proportioning 99:0.5:0.5 mix homogeneously；Silicon nanowire material, CMC (Carboxylic Acid Fibre element sodium), SBR (butadiene-styrene rubber) are suppressed on Copper Foil by after proportioning 97:1:2 mix homogeneously, obtains negative plate；With PE/PP composite diaphragm as ion exchange membrane, use the nonaqueous electrolytic solution C1 of the present embodiment, use this area conventional method to make button cell S1.
Embodiment 2
Using step same as in Example 1 to prepare nonaqueous electrolytic solution and button cell, difference is:
In step (1), by the lithium hexafluoro phosphate (LiPF of 9 weight portions6) be dissolved in the nonaqueous solvent of 90.9 weight portions, it is subsequently adding double (TMS) sulfuric esters (compound as shown in formula (2)) of 0.1 weight portion, prepares non-aqueous electrolyte for lithium ion cell C2 and button cell S2.
Embodiment 3
Using step same as in Example 1 to prepare nonaqueous electrolytic solution and button cell, difference is:
In step (1), by the lithium hexafluoro phosphate (LiPF of 9 weight portions6) be dissolved in the nonaqueous solvent of 90.9 weight portions, it is subsequently adding double (triethyl silyl) sulfuric esters (compound as shown in formula (3)) of 0.1 weight portion, prepares non-aqueous electrolyte for lithium ion cell C3 and button cell S3.
Embodiment 4
Using step same as in Example 1 to prepare nonaqueous electrolytic solution and button cell, difference is:
In step (1), by the LiPF of 10 weight portions6It is dissolved in the nonaqueous solvent of 89 weight portions, it is subsequently adding double (TMS) sulfuric esters (compound as shown in formula (2)) of 0.5 weight portion and double (triethyl silyl) sulfuric esters (compound as shown in formula (3)) of 0.5 weight portion, prepares non-aqueous electrolyte for lithium ion cell C4 and button cell S4.
Embodiment 5-8
Being respectively adopted the method identical with embodiment 1-4 and prepare nonaqueous electrolytic solution and button cell, difference is:
In step (2), use the silicon nanowire material in silicon nanowire material alternate embodiment 1-4 respectively of carbon cladding, obtain button cell S5-S8 successively.
Embodiment 9-12
Being respectively adopted the method identical with embodiment 1-4 step (1) and prepare nonaqueous electrolytic solution, be then injected separately into by nonaqueous electrolytic solution in aluminum hull rectangular cell, the positive electrode of aluminum-shell battery uses LiCoO2, negative material use carbon cladding silicon nanowire material, obtain aluminum-shell battery S9-S12 after assembling successively.
Embodiment 13
Using step same as in Example 1 to prepare nonaqueous electrolytic solution and button cell, difference is:
Step (2) uses graphite substituted for silicon nano-material as negative material, prepare button cell S13.
Embodiment 14
Using method same as in Example 1 to prepare nonaqueous electrolytic solution and button cell, difference is: in step (1), by (lithium hexafluoro phosphate) LiPF of 13 weight portions6It is dissolved in the nonaqueous solvent of 81.9 weight portions, it is subsequently adding double (TMS) sulfuric esters and three (pentafluorophenyl group) borine (TPFPB) of 5 weight portions of 0.1 weight portion, prepares non-aqueous electrolyte for lithium ion cell C14 and button cell S14.
Comparative example 1
Using method same as in Example 1 to prepare nonaqueous electrolytic solution and button cell, difference is: in step (1), directly by the LiPF of 13 weight portions6It is dissolved in the nonaqueous solvent of 87 weight portions, mix homogeneously；Prepare non-aqueous electrolyte for lithium ion cell DC1 and button cell DS1.
Comparative example 2
Using method same as in Example 1 to prepare nonaqueous electrolytic solution and button cell, difference is: in step (1), by (lithium hexafluoro phosphate) LiPF of 13 weight portions6It is dissolved in the nonaqueous solvent of 82 weight portions, is subsequently adding three (pentafluorophenyl group) borine (TPFPB) of 5 weight portions；Prepare non-aqueous electrolyte for lithium ion cell DC2 and button cell DS2.
Comparative example 3-4
Being respectively adopted the method identical with comparative example 1-2 and prepare nonaqueous electrolytic solution and button cell, difference is:
In step (2), use the silicon nanowire material of carbon cladding to substitute the silicon nanowire material in comparative example 1-2 respectively, obtain button cell DS3-DS4 successively.
Comparative example 5-6
Being respectively adopted the method identical with comparative example 1-2 and prepare nonaqueous electrolytic solution, be then injected separately into by nonaqueous electrolytic solution in aluminum hull rectangular cell, the positive electrode of aluminum-shell battery uses LiCoO2, negative material use carbon cladding silicon nanowire material, obtain aluminum-shell battery DS5-DS6 after assembling successively.
Comparative example 7
Using the step identical with comparative example 1 to prepare nonaqueous electrolytic solution and button cell, difference is: uses graphite to replace silicon nanowire material as negative material in step (2), prepares button cell DS7.
Performance test
(1) charge-discharge performance test
By each experiment button cell S1-S8, S13-S14 and DS1-DS4 and DS7 at normal temperatures with the electric current constant-current discharge of 0.1mA to 0.005V, then with 0.1mA constant-current charge to 1.5V, the discharge capacity of record battery and charging capacity, calculate efficiency for charge-discharge (%)=charging capacity/discharge capacity × 100% (PLSCONFM this test whether correctly, if charging and discharging currents to be limited and by voltage).Test result is as shown in table 1.
Table 1
(2) circulating battery test
Each experiment aluminum-shell battery S9-S12 and DS5-DS6 is charged to 4.2V with 200mA constant current constant voltage at normal temperatures, charge cutoff electric current is 20mA, then with 200mA constant-current discharge to 3.0V, record initial charge capacity and discharge capacity, and calculate discharging efficiency (%)；So after repeated charge-discharge cycles 100 times, record the discharge capacity of the 100th circulation, calculate discharge capacity × 100% of the discharge capacity of capability retention (%)=circulation 100 times after circulating/first；And record aluminum-shell battery circulation before and after thickness (PLSCONFM this test whether correctly, if charging and discharging currents to be limited and by voltage).Test result is as shown in table 2.
Table 2
From the test result of upper table 1 it can be seen that embodiment 1-4 and comparative example 1-2 are all to use silicon nanowire material to prepare button cell as negative material, the test data of S1-S4 and DS1-DS2 in each battery charging and discharging test result such as table 1 obtained, as can be seen from the data, with using silicon nanowire material as negative material, the electrolyte that the application of the invention provides, the discharging efficiency minimum 83.26% of the battery prepared, and comparative example is the highest by only 47.10%；Embodiment 5-8 and comparative example 3-4 are all that the silicon nanowire material using carbon cladding prepares button cell as negative material, obtain the test data of S5-S8 and DS3-DS4 in the charge-discharge test result such as table 1 of each battery, as can be seen from the data, with using the silicon nanowire material of carbon cladding as negative material, the electrolyte that the application of the invention provides, the discharging efficiency minimum 92.14% of the battery prepared, and comparative example is up to 73.09%；Embodiment 13 and comparative example 7 are all to use graphite to prepare button cell as negative material, the test data of S13 and DS7 in the charge-discharge test result such as table 1 of each battery prepared, can be seen that the electrolyte that the application of the invention provides, the discharging efficiency of the battery prepared is 88.54%, is far longer than the efficiency for charge-discharge 50.15% of the battery of comparative example 7.
Can be seen that from the test result of table 2, S9-S12 and DS5-DS6 is all that the silicon nanowire material using carbon cladding is prepared as aluminum-shell battery as negative material, it is circulated performance test, be can be seen that by test result, after 100 circulations, the capacity surplus ratio of embodiment is more than 60%, and comparative example is only respectively 36.4% and 47.5%.And the battery of embodiment is far smaller than comparative example battery in its thickness change after 100 circulations.
The charge-discharge performance of lithium ion battery prepared by the embodiment of the present invention and the cycle performance of battery are apparently higher than prior art, the especially charge-discharge performance of silicon cathode lithium ion battery and the improvement of cycle performance is particularly evident, use the non-aqueous electrolyte for lithium ion cell of the present invention for lithium ion battery, the battery obtained not only has a relatively high charge-discharge performance, and after circulation, capability retention is high and before and after circulation, cell deformation is little, battery life is long.
Claims (10)
1. a non-aqueous electrolyte for lithium ion cell, including lithium salts, organic solvent and additive, it is characterised in that
Described additive is structure shown in formula (1):
Wherein, R be carbon number be the alkyl of 1-4.
Non-aqueous electrolyte for lithium ion cell the most according to claim 1, it is characterised in that R is methyl.
Non-aqueous electrolyte for lithium ion cell the most according to claim 1, it is characterised in that R is ethyl.
4. according to the non-aqueous electrolyte for lithium ion cell described in claim 1-3 any one, it is characterised in that with
On the basis of the gross weight of nonaqueous electrolytic solution, the content of described additive is 0.1-2%.
5. according to the non-aqueous electrolyte for lithium ion cell described in claim 1-3 any one, it is characterised in that with
On the basis of the gross weight of nonaqueous electrolytic solution, the content of described additive is 0.5-1.5%.
Non-aqueous electrolyte for lithium ion cell the most according to claim 1, it is characterised in that described nonaqueous solvent
At least one in carboxylic acid esters solvent, carbonate-based solvent, nitrile solvents or ketones solvent.
Non-aqueous electrolyte for lithium ion cell the most according to claim 6, it is characterised in that described nonaqueous solvent
Selected from ethylene carbonate, Allyl carbonate, dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, formic acid
One or more of methyl ester, methyl acetate, methyl propionate, ethyl acetate, adiponitrile or succinonitrile.
Non-aqueous electrolyte for lithium ion cell the most according to claim 7, it is characterised in that described lithium salts is selected from
LiPF6、LiClO4、LiBF4、LiAsF6、LiSiF6、LiAlCl4、LiBOB、LiODFB、LiCl、LiBr、
LiI、LiCF3SO3、、Li(CF3CO2)2N、Li(CF3SO2)2N or Li (SO2C2F5)2One or many in N
Kind.
9. a lithium ion battery, the battery core including housing and being contained in housing, nonaqueous electrolytic solution, battery core includes
Positive pole, negative pole and the barrier film between positive pole and negative pole, described positive pole includes positive electrode active materials, conduction
Agent and binding agent, described negative pole includes that negative active core-shell material and binding agent, described negative active core-shell material are nanometer
Silicon materials, it is characterised in that described nonaqueous electrolytic solution is the nonaqueous electrolytic solution described in any one of claim 1-8.
Lithium ion battery the most according to claim 9, it is characterised in that described nano silicon material is
Silicon nanowire material or the silicon nanowire material of carbon cladding.
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| WO2018120791A1 (en) * | 2016-12-26 | 2018-07-05 | 宁德时代新能源科技股份有限公司 | Electrolyte and secondary battery |
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| CN109390628A (en) * | 2017-08-08 | 2019-02-26 | 张家港市国泰华荣化工新材料有限公司 | A kind of nonaqueous electrolytic solution and lithium ion battery |
| CN110224175A (en) * | 2019-04-23 | 2019-09-10 | 珠海市赛纬电子材料股份有限公司 | A kind of non-aqueous electrolyte for lithium ion cell and the lithium ion battery comprising the electrolyte |
| CN110931860A (en) * | 2018-09-19 | 2020-03-27 | 丰田自动车株式会社 | Nonaqueous electrolyte for lithium ion secondary battery |
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| CN112467215A (en) * | 2020-11-30 | 2021-03-09 | 远景动力技术(江苏)有限公司 | Electrolyte and lithium ion battery |
| CN114142092A (en) * | 2021-11-26 | 2022-03-04 | 常州赛得能源科技有限公司 | Electrolyte, electrochemical device and method for stabilizing positive electrode material |
| CN114556659A (en) * | 2019-10-25 | 2022-05-27 | 三星Sdi株式会社 | Electrolyte for lithium secondary battery and lithium secondary battery including the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1822423A (en) * | 2001-05-11 | 2006-08-23 | 三星Sdi株式会社 | Electrolyte for lithium secondary battery and lithium secondary battery comprising same |
| CN103794781A (en) * | 2014-02-27 | 2014-05-14 | 北京国能电池科技有限公司 | Lithium battery as well as preparation method thereof |
| CN104300174A (en) * | 2014-10-11 | 2015-01-21 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| CN104409686A (en) * | 2014-11-21 | 2015-03-11 | 大连海事大学 | Silicon nanowire composite electrode as well as preparation and application thereof |
-
2015
- 2015-03-31 CN CN201510148518.4A patent/CN106159321A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1822423A (en) * | 2001-05-11 | 2006-08-23 | 三星Sdi株式会社 | Electrolyte for lithium secondary battery and lithium secondary battery comprising same |
| CN103794781A (en) * | 2014-02-27 | 2014-05-14 | 北京国能电池科技有限公司 | Lithium battery as well as preparation method thereof |
| CN104300174A (en) * | 2014-10-11 | 2015-01-21 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| CN104409686A (en) * | 2014-11-21 | 2015-03-11 | 大连海事大学 | Silicon nanowire composite electrode as well as preparation and application thereof |
Cited By (12)
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|---|---|---|---|---|
| WO2018120791A1 (en) * | 2016-12-26 | 2018-07-05 | 宁德时代新能源科技股份有限公司 | Electrolyte and secondary battery |
| WO2018120792A1 (en) * | 2016-12-26 | 2018-07-05 | 宁德时代新能源科技股份有限公司 | Electrolyte and secondary battery |
| CN109390628A (en) * | 2017-08-08 | 2019-02-26 | 张家港市国泰华荣化工新材料有限公司 | A kind of nonaqueous electrolytic solution and lithium ion battery |
| CN109390628B (en) * | 2017-08-08 | 2020-09-01 | 张家港市国泰华荣化工新材料有限公司 | Non-aqueous electrolyte and lithium ion battery |
| CN110931860A (en) * | 2018-09-19 | 2020-03-27 | 丰田自动车株式会社 | Nonaqueous electrolyte for lithium ion secondary battery |
| CN110224175A (en) * | 2019-04-23 | 2019-09-10 | 珠海市赛纬电子材料股份有限公司 | A kind of non-aqueous electrolyte for lithium ion cell and the lithium ion battery comprising the electrolyte |
| CN110224175B (en) * | 2019-04-23 | 2021-05-25 | 珠海市赛纬电子材料股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery comprising same |
| CN114556659A (en) * | 2019-10-25 | 2022-05-27 | 三星Sdi株式会社 | Electrolyte for lithium secondary battery and lithium secondary battery including the same |
| CN111834671A (en) * | 2020-07-27 | 2020-10-27 | 香河昆仑化学制品有限公司 | Electrolyte suitable for silicon-carbon cathode and lithium ion battery |
| CN112054238A (en) * | 2020-09-11 | 2020-12-08 | 山东海科新源材料科技股份有限公司 | Cyclic sulfate additive containing silica chain segment, electrolyte containing cyclic sulfate additive and lithium ion battery |
| CN112467215A (en) * | 2020-11-30 | 2021-03-09 | 远景动力技术(江苏)有限公司 | Electrolyte and lithium ion battery |
| CN114142092A (en) * | 2021-11-26 | 2022-03-04 | 常州赛得能源科技有限公司 | Electrolyte, electrochemical device and method for stabilizing positive electrode material |
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