CN106941191A - Lithium ion battery and its nonaqueous electrolytic solution - Google Patents
Lithium ion battery and its nonaqueous electrolytic solution Download PDFInfo
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- CN106941191A CN106941191A CN201610003632.2A CN201610003632A CN106941191A CN 106941191 A CN106941191 A CN 106941191A CN 201610003632 A CN201610003632 A CN 201610003632A CN 106941191 A CN106941191 A CN 106941191A
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- Prior art keywords
- electrolytic solution
- nonaqueous electrolytic
- lithium ion
- ion battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 73
- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 66
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 32
- 230000000996 additive effect Effects 0.000 claims abstract description 32
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 14
- 238000005868 electrolysis reaction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007774 positive electrode material Substances 0.000 claims description 8
- 239000011258 core-shell material Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 3
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 27
- 229910013075 LiBF Inorganic materials 0.000 description 19
- 239000003792 electrolyte Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 125000004122 cyclic group Chemical group 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 8
- -1 wherein Substances 0.000 description 6
- 229910001428 transition metal ion Inorganic materials 0.000 description 5
- 230000010718 Oxidation Activity Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 206010016766 flatulence Diseases 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 1
- LBZRRXXISSKCHV-UHFFFAOYSA-N [B].[O] Chemical compound [B].[O] LBZRRXXISSKCHV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of nonaqueous electrolytic solution, including：Non-aqueous organic solvent, lithium salts and additive, additive includes LiBF4 and with least one in formula I, the dinitrile compound containing unsaturated bond of formula II, wherein, the one or more of R1, R2, A1, A2 in the aliphatic alkyl with 05 carbon atoms；The one or more of R3, R4, A3, A4 in hydrogen atom, fluorine atom, chlorine atom, alkyl, phenyl.In addition, the invention also discloses a kind of lithium ion battery containing nonaqueous electrolytic solution of the present invention.
Description
Technical field
The invention belongs to field of lithium ion battery, it is more particularly related to a kind of lithium ion battery and
Its nonaqueous electrolytic solution.
Background technology
Lithium ion battery has that energy density is high, operating voltage is high, self-discharge rate is low, had extended cycle life, nothing
Unique advantage such as pollution, is widely used in the electronic products such as camera, mobile phone as power supply.
In recent years, the fast-developing endurance to lithium ion battery of smart electronicses product proposes higher
It is required that, performance of the people using the mode of digital product also to lithium ion battery proposes extra requirement.Example
Such as, when people use notebook computer, after often lithium ion battery is fully charged, full state is continuously in,
When leaving power supply, can just the discharge working method of work, i.e. lithium ion battery of lithium ion battery is that intermittence is filled
Discharge cycles.
In order to improve the energy density of lithium ion battery, exploitation high-voltage lithium ion batteries are one of effective ways.
At present, operating voltage turns into numerous R＆D institutions and business research in more than 4.35V lithium ion battery
Focus.However, under high voltages, positive pole oxidation activity is uprised, nonaqueous electrolytic solution is easily sent out in positive electrode surface
Raw electrochemical oxidation reactions, and then generation gas is decomposed, cause irreversible capacity loss, cause lithium-ion electric
The circulation volume conservation rate in pond declines.
It can be seen that, the stability of negative electrode and electrolyte interface is improved, it is to improve to suppress electrolyte in the decomposition of negative electrode
The high-temperature storage performance of high-voltage lithium ion batteries, the key point of cycle performance.Especially for intermittence
Charge and discharge cycles, extend the time of lithium ion battery high-voltage fully charged state storage, cloudy to lithium ion battery
The interface stability of pole and electrolyte proposes higher requirement.
In view of this, it is a kind of with preferable high-temperature storage performance and the holding of intermittent cyclic capacity it is necessory to provide
The lithium ion battery and its nonaqueous electrolytic solution of rate.
The content of the invention
It is an object of the invention to：A kind of lithium ion battery and its nonaqueous electrolytic solution are provided, there is reason to obtain
Think the lithium ion battery of high-temperature storage performance and intermittent cyclic capability retention.
In order to realize foregoing invention purpose, the invention provides a kind of nonaqueous electrolytic solution, it includes non-aqueous organic
Solvent, lithium salts and additive, wherein, additive include LiBF4 and with formula I, formula II containing not
At least one in the dinitrile compound of saturated bond,
Wherein, R1, R2, A1, A2 in the aliphatic alkyl with 0-5 carbon atom one
Plant or several；R3, R4, A3, A4 are independently selected from hydrogen atom, fluorine atom, chlorine atom, alkyl, benzene
One or more in base.
Improved as one kind of nonaqueous electrolytic solution of the present invention, the dinitrile compound of Formulas I is Isosorbide-5-Nitrae-dicyano -2- fourths
Alkene, the dinitrile compound of Formula II is 2,4- dicyano -1- butylene.
Improved as one kind of nonaqueous electrolytic solution of the present invention, formula I, the dinitrile compound of formula II are in non-aqueous solution electrolysis
Weight/mass percentage composition in liquid is 0.1%~3%, preferably 0.5%~2%.When the dinitrile compound of formula I or formula II
When weight/mass percentage composition in nonaqueous electrolytic solution is less than 0.1%, it is limited in the absorption and polymerization of positive electrode surface,
Transition metal ions dissolution can not effectively be suppressed, suppress oxidation Decomposition of the electrolyte in positive pole；When formula I or formula
When weight/mass percentage composition of II dinitrile compound in nonaqueous electrolytic solution is higher than 3%, itself and positive electrode active materials
In transition metal formation complexing layer it is blocked up, and produce substantial amounts of polymer and can seriously increase lithium ion
The impedance of battery, is unfavorable for the dynamic performance and circulation volume conservation rate of lithium ion battery.
Improved as one kind of nonaqueous electrolytic solution of the present invention, LiBF4 (LiBF4) in nonaqueous electrolytic solution
Weight/mass percentage composition is 0.01%~0.5%.Work as LiBF4Weight/mass percentage composition in nonaqueous electrolytic solution is less than
When 0.01%, its improvement result to positive pole is not obvious；Work as LiBF4Quality percentage in nonaqueous electrolytic solution contains
When amount is higher than 0.5%, excessive LiBF4The impedance of lithium ion battery can be increased, be unfavorable for lithium ion battery
Circulation volume conservation rate.
Improved as one kind of nonaqueous electrolytic solution of the present invention, the lithium salts is selected from LiPF6、LiClO4、LiAsF6、
LiN(CF3SO2)2、LiCF3SO3, one or more in LiBOB.
As nonaqueous electrolytic solution of the present invention one kind improve, the non-aqueous organic solvent be selected from ethylene carbonate,
Propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, methyl formate,
One or more in Ethyl formate, ethyl propionate, propyl propionate, tetrahydrofuran.
In order to realize foregoing invention purpose, present invention also offers a kind of lithium ion battery, it includes：
Positive plate, including plus plate current-collecting body and be arranged on plus plate current-collecting body and containing positive electrode active materials just
Pole diaphragm；
Negative plate, including negative current collector and be arranged at negative on negative current collector and containing negative active core-shell material
Pole diaphragm；
Barrier film, is interval between positive plate and negative plate；
Nonaqueous electrolytic solution；And
Package foil；
Wherein, the nonaqueous electrolytic solution is foregoing nonaqueous electrolytic solution.
Improved as one kind of lithium ion battery of the present invention, the end of charge voltage of the lithium ion battery is
4.35V~5V.
Improved as one kind of lithium ion battery of the present invention, the positive electrode active materials include cobalt acid lithium and/or lithium
Nickel manganese cobalt ternary material.
Improved as one kind of lithium ion battery of the present invention, the negative active core-shell material includes graphite and/or silicon.
Compared with prior art, LiBF is added simultaneously in nonaqueous electrolytic solution of the present invention4With the two of formula I or formula II
Nitrile compound, the two collaboration can stablize cathode surface oxygen atom and transition metal ions in cathode surface film forming,
Reduce the oxidation activity under cathode high voltage and reduce transition metal ions dissolution, be effectively improved lithium ion battery
High-temperature storage performance and intermittent cyclic capability retention：On the one hand, LiBF4It is anti-in surface of positive electrode active material
The boron-oxygen that should be generated can improve the stability of oxygen atom in positive electrode active materials under high voltage, and reduction is high
The electro-chemical activity of cathode surface under voltage, suppresses oxidation Decomposition of the electrolyte in cathode surface；On the other hand,
In two nitrile compounds containing unsaturated bond of formula I or formula II, many itrile groups can be with cathode material surface transition
Metal ion forms multiple tooth complex compound, is conducive to suppressing transition metal ions dissolution, unsaturated double-bond occurs poly-
Reaction is closed, finer and close protective layer is formed；LiBF4Acted synergistically with the dinitrile compound of formula I or formula II, can
Effectively improve cathode surface stability, suppress high voltage under electrolyte cathode surface reaction, and then
The problem of suppressing high-temperature lithium ion battery storage aerogenesis and lithium ion battery interval charge and discharge cycles capacity attenuation.
Embodiment
In order that the purpose of the present invention, technical scheme and technique effect become apparent from understanding, below in conjunction with implementation
The present invention will be described in further detail with comparative example for example.It should be appreciated that described in this specification
Embodiment and comparative example are not intended to limit the present invention just for the sake of explaining the present invention.
Comparative example 1
(1) preparation of nonaqueous electrolytic solution
In drying shed, EC in mass ratio:DEC=3:7 weigh non-aqueous organic solvent and mix, and add afterwards
LiPF6As lithium salts and make LiPF6Concentration be 1mol/L, obtain nonaqueous electrolytic solution.
(2) preparation of positive plate
It is 10% to weigh 1.42kg Solvents N-methyls -2-Pyrrolidone (NMP), 1.2kg weight/mass percentage compositions
Binding agent polyvinylidene fluoride (PVDF), 0.16kg conductive agents electrically conductive graphite and 7.2kg positive electrode active materials
LiCoO2It is sufficiently mixed stirring and obtains anode sizing agent, anode sizing agent is uniformly coated to thickness for 16 μm afterwards
Plus plate current-collecting body aluminium foil on, afterwards 120 DEG C toast 1h obtain positive pole diaphragm, afterwards through overcompaction, point
Cut and obtain positive plate.
(3) preparation of negative plate
Weigh 1.2Kg weight/mass percentage compositions be 1.5% thickener sodium carboxymethylcellulose (CMC) solution,
Binding agent SBR emulsion, 2.4kg negative active core-shell material graphite powders that 0.07kg weight/mass percentage compositions are 50%
End is sufficiently mixed stirring and obtains cathode size, and it is negative for 12 μm that cathode size is uniformly coated into thickness afterwards
On the copper foil of affluxion body of pole, afterwards 120 DEG C toast 1h obtain cathode membrane, afterwards through overcompaction, cut
To negative plate.
(4) preparation of lithium ion battery
Above-mentioned positive plate, negative plate are separated with thickness for 12 μm of polypropylene barrier film and squarely is wound
Naked battery core, aluminum foil sack is loaded afterwards, 80 DEG C baking water removal after, injection nonaqueous electrolytic solution, sealing,
Chemical conversion, exhaust and test capacity obtain the lithium ion battery of finished product.
Comparative example 2
Method according to comparative example 1 prepares lithium ion battery, the difference is that only：In nonaqueous electrolytic solution also
Containing additive, the LiBF that additive is 0.2% for the weight/mass percentage composition in nonaqueous electrolytic solution4。
Comparative example 3
Method according to comparative example 1 prepares lithium ion battery, the difference is that only：In nonaqueous electrolytic solution also
Containing additive, additive is 1% to have a Formulas I structure for weight/mass percentage composition in nonaqueous electrolytic solution
Dinitrile compound.
Comparative example 4
Method according to comparative example 1 prepares lithium ion battery, the difference is that only：In nonaqueous electrolytic solution also
Containing additive, the LiBF that additive is 0.6% for the weight/mass percentage composition in nonaqueous electrolytic solution4With non-
The dinitrile compound with Formulas I structure that weight/mass percentage composition in water electrolysis liquid is 1%.
Comparative example 5
Method according to comparative example 1 prepares lithium ion battery, the difference is that only：In nonaqueous electrolytic solution also
Containing additive, the LiBF that additive is 0.2% for the weight/mass percentage composition in nonaqueous electrolytic solution4With non-
The dinitrile compound with Formulas I structure that weight/mass percentage composition in water electrolysis liquid is 4%.
Embodiment 1
Method according to comparative example 1 prepares lithium ion battery, the difference is that only：In nonaqueous electrolytic solution also
Containing additive, the LiBF that additive is 0.1% for the weight/mass percentage composition in nonaqueous electrolytic solution4With non-
The dinitrile compound with Formulas I structure that weight/mass percentage composition in water electrolysis liquid is 1%.
Embodiment 2
Method according to comparative example 1 prepares lithium ion battery, the difference is that only：In nonaqueous electrolytic solution also
Containing additive, the LiBF that additive is 0.2% for the weight/mass percentage composition in nonaqueous electrolytic solution4With non-
The dinitrile compound with Formulas I structure that weight/mass percentage composition in water electrolysis liquid is 1%.
Embodiment 3
Method according to comparative example 1 prepares lithium ion battery, the difference is that only：In nonaqueous electrolytic solution also
Containing additive, the LiBF that additive is 0.3% for the weight/mass percentage composition in nonaqueous electrolytic solution4With non-
The dinitrile compound with Formulas I structure that weight/mass percentage composition in water electrolysis liquid is 1%.
Embodiment 4
Method according to comparative example 1 prepares lithium ion battery, the difference is that only：In nonaqueous electrolytic solution also
Containing additive, the LiBF that additive is 0.5% for the weight/mass percentage composition in nonaqueous electrolytic solution4With non-
The dinitrile compound with Formulas I structure that weight/mass percentage composition in water electrolysis liquid is 1%.
Embodiment 5
Method according to comparative example 1 prepares lithium ion battery, the difference is that only：In nonaqueous electrolytic solution also
Containing additive, the LiBF that additive is 0.2% for the weight/mass percentage composition in nonaqueous electrolytic solution4With non-
The dinitrile compound with Formulas I structure that weight/mass percentage composition in water electrolysis liquid is 0.5%.
Embodiment 6
Method according to comparative example 1 prepares lithium ion battery, the difference is that only：In nonaqueous electrolytic solution also
Containing additive, the LiBF that additive is 0.2% for the weight/mass percentage composition in nonaqueous electrolytic solution4With non-
The dinitrile compound with Formulas I structure that weight/mass percentage composition in water electrolysis liquid is 2%.
Embodiment 7
Method according to comparative example 1 prepares lithium ion battery, the difference is that only：In nonaqueous electrolytic solution also
Containing additive, the LiBF that additive is 0.2% for the weight/mass percentage composition in nonaqueous electrolytic solution4With non-
The dinitrile compound with Formulas I structure that weight/mass percentage composition in water electrolysis liquid is 3%.
Embodiment 8
Method according to comparative example 1 prepares lithium ion battery, the difference is that only：In nonaqueous electrolytic solution also
Containing additive, the LiBF that additive is 0.2% for the weight/mass percentage composition in nonaqueous electrolytic solution4With non-
Weight/mass percentage composition in water electrolysis liquid is that 0.5% dinitrile compound with Formulas I structure and quality percentage contain
Measure the dinitrile compound with Formula II structure for 0.5%.
Embodiment 9
Method according to comparative example 1 prepares lithium ion battery, the difference is that only：In nonaqueous electrolytic solution also
Containing additive, the LiBF that additive is 0.2% for the weight/mass percentage composition in nonaqueous electrolytic solution4With non-
The dinitrile compound with Formula II structure that weight/mass percentage composition in water electrolysis liquid is 1%.
Table 1 is the electrolyte addition manner of each comparative example and embodiment.
The electrolyte addition manner of table 1
Comparative example 1-5 and embodiment 1-9 performance test process and test result
(1) high-temperature storage performance of lithium ion battery is tested
At 25 DEG C, with 0.5C multiplying powers constant-current charge to 4.4V, afterwards under 4.4V constant-voltage charge to 0.05C,
Test the thickness of lithium ion battery and be designated as h0；Lithium ion battery is put into 60 DEG C of insulating box afterwards, is incubated
30 days, and tested the thickness of lithium ion battery every 5 days and be designated as hn, n is that high-temperature lithium ion battery is stored
Number of days.
High-temperature lithium ion battery store n days after thickness swelling (%)=(hn-h0)/h0 × 100%.
(2) the intermittent cyclic performance test of lithium ion battery
45 DEG C of volume tests：At 45 DEG C, lithium ion battery is stood 30 minutes, afterwards with 0.5C multiplying powers
Constant-current charge is to 4.4V, and constant-voltage charge, to 0.05C, and stands 5 minutes under 4.4V afterwards, afterwards with 0.5C
Multiplying power constant-current discharge records battery initial discharge capacity C0 to 3.0V；
45 DEG C of intermittent cyclic tests：At 45 DEG C, lithium ion battery is stood 30 minutes；With 0.5C multiplying powers
Constant-current charge is to 4.4V, and constant-voltage charge is to 0.05C under 4.4V；It is small that battery stands 20 in 45 DEG C of environment
When；Battery records discharge capacity of the cell with 0.5C multiplying powers Model For Transverse-discharge Flow Type to 3.0V；This is between one complete
Have a rest charge and discharge cycles, battery charge and discharge cycles 120 times in the same manner.
The discharge capacity of capability retention (%)=n-th circulation after the n-th circulation of lithium ion battery/first
Discharge capacity × 100%.
The storage test of lithium ion battery and intermittent cyclic test result are as shown in table 2.
The battery storage of table 2 is tested and intermittent cyclic test result
It can be seen that from comparative example 1-3 and embodiment 2 test result and be individually added into the electrolytic solution quality hundred
Divide the LiBF that content is 0.2%4Or weight/mass percentage composition is the dinitrile compound of 1% Formulas I structure, lithium ion
The high-temperature storage performance of battery under high voltages has certain improvement, but effect is not notable, and the interval of battery is followed
Ring performance also has certain improvement, but is recycled to the failure of latter stage battery core flatulence.And in embodiment 2, electrolyte
In simultaneously add weight/mass percentage composition be 0.2% LiBF4It is the two of 1% Formulas I structure with weight/mass percentage composition
Nitrile compound, the storage performance of lithium ion battery under high voltages improves notable, and battery stores 30 at 60 DEG C
Its thickness swelling is smaller, is not apparent from flatulence, and lithium ion battery intermittent cyclic capability retention is also obviously improved.
LiBF is added in electrolyte4Boron-oxygen can be generated in negative electrode, reduce the oxidation activity of negative electrode；Electrolyte
The middle dinitrile compound for adding Formulas I structure, can be complexed and aggregate into the protective layer of densification, suppression in cathode surface
Reaction of the electrolyte processed in negative electrode.Therefore it is individually added into LiBF in electrolyte4Or the dinitrile compound of Formulas I structure
The stability of negative electrode and electrolyte interface under high voltage can be improved, improve the high temperature storage of lithium ion battery
Can be with intermittent cyclic capability retention；LiBF is added in electrolyte simultaneously4With the dinitrile compound of Formulas I structure,
In LiBF4While reducing that negative electrode is to the oxidation activity of electrolyte under high voltage, the dinitrile compound of Formulas I structure
Fine and close protective layer is generated, the stability of negative electrode and electrolyte interface is more efficiently improved, improves lithium
The high-temperature storage performance and intermittent cyclic capability retention of ion battery.
Addition quality percentage in the electrolytic solution is can be seen that from embodiment 1-4 and comparative example 4 test result to contain
Measure after the dinitrile compound for 1% Formulas I structure, while adding the LiBF of different quality percentage composition4, lithium
The high-temperature storage performance of ion battery is with LiBF4Content increase and improve, still, LiBF4Content reaches
When 0.6% (comparative example 4), the intermittent cyclic capability retention of lithium ion battery is significantly reduced.Therefore, LiBF4
Addition be preferably 0.1%~0.3%.
It can be seen that and add in the electrolytic solution from embodiment 5-8, embodiment 2 and comparative example 5 test result
Weight/mass percentage composition is 0.2% LiBF4Afterwards, at the same add different quality percentage composition have Formulas I structure
Dinitrile compound, the high-temperature storage performance of lithium ion battery is with the increasing of the dinitrile compound content of Formulas I structure
Plus and improve, still, when the content of the dinitrile compound of Formulas I structure reaches 4% (comparative example 5), lithium ion
The intermittent cyclic capability retention of battery declines rapidly with cycle-index.Therefore, the dinitrile compound of Formulas I structure
Content in the electrolytic solution is preferably 0.5%~2%.Contrasted from the test result of embodiment 8-9 and embodiment 2
As can be seen that Formula II structure dinitrile compound substitution or part substitution Formulas I structure dinitrile compound and
LiBF4Be added to simultaneously in electrolyte, can play similar improvement high-temperature storage performance of lithium ion battery and
Have a rest the effect of cycle performance.
In summary, LiBF is added simultaneously in nonaqueous electrolytic solution4With two nitrilations with formula I and/or formula II
Compound can make lithium ion battery under high voltages while having preferable high-temperature storage performance and intermittent cyclic capacity
Conservation rate.
According to above-mentioned principle, the present invention can also carry out appropriate change and modification to above-described embodiment.Therefore,
The invention is not limited in specific embodiment disclosed and described above, to some modifications and changes of the present invention
It should also be as falling into the scope of the claims of the present invention.Although in addition, having used one in this specification
A little specific terms, but these terms are merely for convenience of description, do not constitute any limitation to the present invention.
Claims (10)
1. a kind of nonaqueous electrolytic solution, including non-aqueous organic solvent, lithium salts and additive, it is characterised in that institute
Stating additive includes：LiBF4 and with formula I, the dinitrile compound containing unsaturated bond of formula II
At least one,
Wherein, R1, R2, A1, A2 in the aliphatic alkyl with 0-5 carbon atom one
Plant or several；R3, R4, A3, A4 are independently selected from hydrogen atom, fluorine atom, chlorine atom, alkyl, benzene
One or more in base.
2. nonaqueous electrolytic solution according to claim 1, it is characterised in that the dinitrile compound of Formulas I is
Isosorbide-5-Nitrae-dicyano -2- butylene, the dinitrile compound of Formula II is 2,4- dicyano -1- butylene.
3. nonaqueous electrolytic solution according to claim 1, it is characterised in that the dintrile of formula I and/or formula II
Weight/mass percentage composition of the compound in nonaqueous electrolytic solution is 0.1%~3%, preferably 0.5%~2%.
4. nonaqueous electrolytic solution according to claim 1, it is characterised in that LiBF4 is in non-water power
It is 0.01%~0.5% to solve the weight/mass percentage composition in liquid.
5. nonaqueous electrolytic solution according to claim 1, it is characterised in that the lithium salts is selected from LiPF6、
LiClO4、LiAsF6、LiN(CF3SO2)2、LiCF3SO3, one or more in LiBOB.
6. nonaqueous electrolytic solution according to claim 1, it is characterised in that the non-aqueous organic solvent choosing
From ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-Ding Nei
One or more in ester, methyl formate, Ethyl formate, ethyl propionate, propyl propionate, tetrahydrofuran.
7. a kind of lithium ion battery, including：
Positive plate, including plus plate current-collecting body and be arranged on plus plate current-collecting body and containing positive electrode active materials just
Pole diaphragm；
Negative plate, including negative current collector and be arranged at negative on negative current collector and containing negative active core-shell material
Pole diaphragm；
Barrier film, is interval between positive plate and negative plate；
Nonaqueous electrolytic solution；And
Package foil；
Characterized in that, the nonaqueous electrolytic solution is the non-aqueous solution electrolysis any one of claim 1 to 6
Liquid.
8. lithium ion battery according to claim 7, it is characterised in that the lithium ion battery fills
Electric final voltage is 4.35V~5V.
9. lithium ion battery according to claim 7, it is characterised in that the positive electrode active materials bag
Include cobalt acid lithium and/or lithium-nickel-manganese-cobalt ternary material.
10. lithium ion battery according to claim 7, it is characterised in that the negative active core-shell material bag
Include graphite and/or silicon.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108232300A (en) * | 2018-01-05 | 2018-06-29 | 宁德新能源科技有限公司 | A kind of lithium ion battery and its electrolyte |
| CN112400249A (en) * | 2020-03-24 | 2021-02-23 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device |
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| CN102820484A (en) * | 2011-06-08 | 2012-12-12 | 索尼公司 | Nonaqueous electrolyte, nonaqueous electrolyte battery, and battery pack using nonaqueous electrolyte battery |
| CN103000945A (en) * | 2012-11-29 | 2013-03-27 | 惠州Tcl金能电池有限公司 | Electrolyte and application thereof |
| CN103229342A (en) * | 2010-11-30 | 2013-07-31 | 株式会社Lg化学 | lithium rechargeable battery |
| CN103354962A (en) * | 2011-02-10 | 2013-10-16 | 三菱化学株式会社 | Non-aqueous electrolyte for secondary battery, and non-aqueous electrolyte secondary battery using same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103229342A (en) * | 2010-11-30 | 2013-07-31 | 株式会社Lg化学 | lithium rechargeable battery |
| CN103354962A (en) * | 2011-02-10 | 2013-10-16 | 三菱化学株式会社 | Non-aqueous electrolyte for secondary battery, and non-aqueous electrolyte secondary battery using same |
| CN102820484A (en) * | 2011-06-08 | 2012-12-12 | 索尼公司 | Nonaqueous electrolyte, nonaqueous electrolyte battery, and battery pack using nonaqueous electrolyte battery |
| CN103000945A (en) * | 2012-11-29 | 2013-03-27 | 惠州Tcl金能电池有限公司 | Electrolyte and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108232300A (en) * | 2018-01-05 | 2018-06-29 | 宁德新能源科技有限公司 | A kind of lithium ion battery and its electrolyte |
| CN112400249A (en) * | 2020-03-24 | 2021-02-23 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device |
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