CN104282939B - A kind of high voltage electrolyte of lithium ion battery - Google Patents
A kind of high voltage electrolyte of lithium ion battery Download PDFInfo
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- CN104282939B CN104282939B CN201310276370.3A CN201310276370A CN104282939B CN 104282939 B CN104282939 B CN 104282939B CN 201310276370 A CN201310276370 A CN 201310276370A CN 104282939 B CN104282939 B CN 104282939B
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- lithium
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- ion battery
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 63
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 29
- 239000003960 organic solvent Substances 0.000 claims abstract description 26
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 25
- 239000010452 phosphate Substances 0.000 claims abstract description 25
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 22
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 18
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000012046 mixed solvent Substances 0.000 claims abstract description 4
- -1 wherein Substances 0.000 claims abstract description 4
- BKIWAQYWKUFSRE-UHFFFAOYSA-N prop-1-ene;sulfuric acid Chemical group CC=C.OS(O)(=O)=O BKIWAQYWKUFSRE-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 6
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical group CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 6
- 229910001290 LiPF6 Inorganic materials 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000005030 aluminium foil Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- XESSXNRXAYFGSO-UHFFFAOYSA-N B([O-])([O-])[O-].[Li+].C(C(=O)O)(=O)O.[Li+].[Li+] Chemical compound B([O-])([O-])[O-].[Li+].C(C(=O)O)(=O)O.[Li+].[Li+] XESSXNRXAYFGSO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910011279 LiCoPO4 Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- LXRYWGXWAXCTJD-UHFFFAOYSA-N [Li+].B([O-])([O-])O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] Chemical class [Li+].B([O-])([O-])O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] LXRYWGXWAXCTJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229940063013 borate ion Drugs 0.000 description 1
- MPDCKIORILZMHV-UHFFFAOYSA-N boric acid;lithium;oxalic acid Chemical compound [Li].OB(O)O.OC(=O)C(O)=O MPDCKIORILZMHV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 210000000720 eyelash Anatomy 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 210000004508 polar body Anatomy 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of high voltage electrolyte of lithium ion battery, it is by organic solvent, electrolyte lithium salt and cathode film formation additive composition, wherein, organic solvent is the mixed solvent of fluorinated ethylene carbonate, three fluoropropylene carbonates and hydrofluoroether composition, and the electrolyte lithium salt is the mixing lithium salts that lithium hexafluoro phosphate and di-oxalate lithium borate are constituted.The present invention efficiently solves that fluorinated solvents viscosity is high and electrolyte lithium salt is the problem of dissolubility is poor in fluorinated organic solvent, fluorinated organic solvent is used directly as the organic solvent in lithium-ion battery electrolytes, and the present invention has wider electrochemical window and preferable resistance to oxidation and high pressure resistant property, there is higher electrical conductivity simultaneously, it can guarantee that the high magnification and power characteristic of electrokinetic cell, also there is higher security, the security performance of electrokinetic cell can be greatly improved.
Description
Technical field
The present invention relates to a kind of lithium-ion battery electrolytes, more particularly, to a kind of high voltage electrolyte of lithium ion battery.
Background technology
Anode material for lithium-ion batteries such as cobalt acid lithium（LiCoO2）, LiFePO4（LiFePO4）And LiMn2O4（LiMn2O4）
Operating voltage be below 4V, and with nickel ion doped（LiNi0.5Mn1.5O4）And cobalt phosphate lithium（LiCoPO4）It is representative Deng material
The discharge voltage of novel high voltage positive electrode may be up to 5V or so, these high voltage materials, which are used for lithium ion battery, to be carried
The output voltage and power density of high battery, further widen the scope of application of the lithium ion battery in high-power electric appliance equipment,
So as to by the extensive concern of researcher in the industry.
But the electrolyte being adapted with high voltage material is there is no at present, and conventional carbonate solvent is constituted with lithium hexafluoro phosphate
Electrolyte ties up to more than 4.5V and will decomposed, so as to cause the decline of whole battery system performance, this just causes new
The exploitation of high pressure material is restricted because lacking stable high-voltage electrolyte, therefore exploitation high voltage electrolyte of lithium ion battery is compeled
In the eyebrows and eyelashes.
Application publication number CN102569888A, data of publication of application 2012.07.11 Chinese patent disclose a kind of for lithium
High-voltage electrolyte of ion battery and preparation method thereof, it includes non-aqueous organic solvent, lithium salts and additive, the additive bag
Include a）Formula below（1）Shown compound, and b）Selected from following compound：Sulfone-based compound, fluoric compound, acid anhydrides and
Ether compound, and its mixture：
Wherein R1For C1~C10Alkyl, C1~C10Alkoxy, or C6~C10Aryl, preferably methyl, ethyl or methoxyl group, X are halogen
Element, and m and n is 1 ~ 5 integer, wherein m+n is less than or equal to 5.The electrolyte is each by being added in conventional carbonate solvent
Additive is planted to improve the high pressure resistant property of electrolyte, it is disadvantageous in that, added with sulfone-based compound in additive, and sulfone
The compatibility of based compound and graphite cathode is very poor, causes the cycle performance of battery poor, in addition, being added in the electrolyte a large amount of
Additive, substantial amounts of additive can not only improve the viscosity of electrolyte, so that the electrical conductivity of electrolyte is reduced, times of influence battery
Rate characteristic, can also influence the capacitance of battery.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of high voltage electrolyte of lithium ion battery, efficiently solve fluoro
Solvent viscosity height and electrolyte lithium salt are in fluorinated organic solvent the problem of dissolubility difference so that fluorinated organic solvent can be straight
Connect and used as the organic solvent in lithium-ion battery electrolytes, and it is of the invention with wider electrochemical window and preferably resistance to
Oxidation and high pressure resistant property, while having higher electrical conductivity, can guarantee that the high magnification and power characteristic of electrokinetic cell, also have
Higher security, can greatly improve the security performance of electrokinetic cell.
To achieve these goals, the present invention uses following technical scheme：
A kind of high voltage electrolyte of lithium ion battery, the high-voltage electrolyte by organic solvent, electrolyte lithium salt and negative pole into
Film additive is constituted, wherein, organic solvent is the mixing of fluorinated ethylene carbonate, three fluoropropylene carbonates and hydrofluoroether composition
Solvent, the electrolyte lithium salt is the mixing lithium salts that lithium hexafluoro phosphate and di-oxalate lithium borate are constituted.Because fluorine atom has by force
Electronegativity and low pole, cause fluorinated solvents to have higher electrochemical stability, but fluorinated solvents have very big viscosity, meeting
The electrical conductivity of electrolyte is substantially reduced, while electrolyte lithium salt, especially LiPF6Dissolubility in fluorinated solvents is poor, therefore
So that current fluorinated solvents are mostly as cosolvent or additive application in lithium ion battery liquid electrolyte, and can not be direct
Applied as solvent.The present invention is used as the organic solvent of electrolyte, fluorinated ethylene carbonate using fluorinated organic solvent
（FEC）, three fluoropropylene carbonates（TEPC）And hydrofluoroether（HFE）Good heat endurance is respectively provided with, safety is nonflammable, and
Compatibility between three is good, and hydrofluoroether has low surface tension, and low viscosity, good wetability plays a part of dispersant,
With fluorinated ethylene carbonate, three fluoropropylene carbonates are mixed to form after mixed solvent can substantially reduce the viscosity of organic solvent,
Dissolubility of the electrolyte lithium salt in the mixed solvent can also be improved simultaneously, efficiently solves that fluorinated solvents viscosity is low and electrolyte
Lithium salts is in fluorinated organic solvent the problem of dissolubility difference so that fluorinated organic solvent can be electrolysed directly as lithium ion battery
Organic solvent in liquid is used；The mixing that electrolyte lithium salt in the present invention is constituted using lithium hexafluoro phosphate and di-oxalate lithium borate
Lithium salts, why using lithium hexafluoro phosphate and di-oxalate lithium borate, its reason is as follows：Lithium hexafluoro phosphate（LiPF6）It is thermally-stabilised
Property it is poor, at relatively high temperatures decompose can produce phosphorus pentafluoride（PF5）, phosphorus pentafluoride has for moisture micro in electrolyte
Higher hydrolytic susceptibility, HF can be produced to corrode plus plate current-collecting body aluminium foil by meeting water, reduce the cycle performance of battery, while by
In the raising of charging voltage, easily there is structural aberration in discharge and recharge system in positive electrode, and the moon in di-oxalate lithium borate
Ion energy and Al3+Reaction forms highly stable network structure passivating film, can not only prevent cathode material structure from changing, and improves just
The high pressure resistant property of polar body system, may also suppress corrosion of the HF to aluminium foil, and di-oxalate lithium borate can also improve the electricity of electrolyte in addition
Conductance, the coordinated of the invention by lithium hexafluoro phosphate and di-oxalate lithium borate, to ensure the electrical conductivity and battery of electrolyte
Cycle performance；The present invention efficiently solves fluorinated solvents viscosity high and electric by the mutual synergy between each component
Solution matter lithium salts is in fluorinated organic solvent the problem of dissolubility difference so that fluorinated organic solvent can be directly as lithium ion battery
Organic solvent in electrolyte is used, and also efficiently solves the problem of HF is to the corrosion of aluminium foil, and the present invention has wider electrification
Window and preferable resistance to oxidation and high pressure resistant property are learned, while having higher electrical conductivity, the high magnification of electrokinetic cell is can guarantee that
And power characteristic, also with higher security, the security performance of electrokinetic cell can be greatly improved.
Preferably, in organic solvent, fluorinated ethylene carbonate：Three fluoropropylene carbonates：The volume ratio of hydrofluoroether is 2
~3：4~7：1~3.Fluorinated ethylene carbonate：Three fluoropropylene carbonates：The volume ratio of hydrofluoroether is 2 ~ 3：4~7：1 ~ 3, You Jirong
The viscosity performance of agent is optimal.
Preferably, in high-voltage electrolyte, the lithium hexafluoro phosphate molar concentration is 0.8 ~ 1.2mol/L, described pair of oxalic acid
Lithium borate molar concentration is 0.1 ~ 0.2mol/L.Lithium hexafluoro phosphate molar concentration is 0.8 ~ 1.2mol/L, described pair of oxalic acid boric acid
Lithium molar concentration is 0.1 ~ 0.2mol/L, and the viscosity and electrical conductivity of electrolyte are good.
Preferably, on the basis of high-voltage electrolyte gross mass, the addition of cathode film formation additive is 1 ~ 2%.
Preferably, the cathode film formation additive is propylene sulfite.Propylene sulfite not only contributes to negative pole
The formation of SEI films, so as to improve the high temperature cyclic performance of battery, can also improve the dissolving of di-oxalate lithium borate in the electrolytic solution
Property, be conducive to improving the electrical conductivity of electrolyte.
Therefore, the present invention has the advantages that：
（1）The present invention is made by the mutual collaboration between fluorinated ethylene carbonate, three fluoropropylene carbonates and hydrofluoroether
With efficiently solving that fluorinated solvents viscosity is high and electrolyte lithium salt be the problem of dissolubility is poor in fluorinated organic solvent so that
Fluorinated organic solvent can be used directly as the organic solvent in lithium-ion battery electrolytes；
（2）By the coordinated of lithium hexafluoro phosphate and di-oxalate lithium borate, it can not only prevent cathode material structure from changing,
The high pressure resistant property of positive pole system is improved, the problem of HF is to the corrosion of aluminium foil is also efficiently solved, it is ensured that the conductance of electrolyte
The cycle performance of rate and battery；
（3）The present invention has wider electrochemical window and preferable resistance to oxidation and high pressure resistant property, while having higher
Electrical conductivity, can guarantee that the high magnification and power characteristic of electrokinetic cell, also with higher security, power electric can be greatly improved
The security performance in pond.
Brief description of the drawings
Fig. 1 is the high-voltage electrolyte of the embodiment of the present invention 1 and the conventional electrolysis liquid LSV curve comparison figures of comparative example.
Embodiment
The present invention will be further described with reference to the accompanying drawings and detailed description.
In the present invention, all devices and raw material are commercially available or the industry is conventional.
Embodiment 1
By fluorinated ethylene carbonate, three fluoropropylene carbonates, hydrofluoroether, lithium hexafluoro phosphate, di-oxalate lithium borate and Asia
Sulfuric acid propylene, which is uniformly mixed according to a ratio, produces high-voltage electrolyte, wherein, fluorinated ethylene carbonate：Three fluoropropylene carbonates：
The volume ratio of hydrofluoroether is 2：4：1, lithium hexafluoro phosphate molar concentration is 0.8mol/L, and di-oxalate lithium borate molar concentration is
0.1mol/L, the addition of propylene sulfite is 1%.
Embodiment 2
By fluorinated ethylene carbonate, three fluoropropylene carbonates, hydrofluoroether, lithium hexafluoro phosphate, di-oxalate lithium borate and Asia
Sulfuric acid propylene, which is uniformly mixed according to a ratio, produces high-voltage electrolyte, wherein, fluorinated ethylene carbonate：Three fluoropropylene carbonates：
The volume ratio of hydrofluoroether is 5：10：4, lithium hexafluoro phosphate molar concentration is 1mol/L, and di-oxalate lithium borate molar concentration is
0.15mol/L, the addition of propylene sulfite is 1.5%.
Embodiment 3
By fluorinated ethylene carbonate, three fluoropropylene carbonates, hydrofluoroether, lithium hexafluoro phosphate, di-oxalate lithium borate and Asia
Sulfuric acid propylene, which is uniformly mixed according to a ratio, produces high-voltage electrolyte, wherein, fluorinated ethylene carbonate：Three fluoropropylene carbonates：
The volume ratio of hydrofluoroether is 3：7：3, lithium hexafluoro phosphate molar concentration is 1.2mol/L, and di-oxalate lithium borate molar concentration is
0.2mol/L, the addition of propylene sulfite is 2%.
Embodiment 4
By fluorinated ethylene carbonate, three fluoropropylene carbonates, hydrofluoroether, lithium hexafluoro phosphate, di-oxalate lithium borate and Asia
Sulfuric acid propylene, which is uniformly mixed according to a ratio, produces high-voltage electrolyte, wherein, fluorinated ethylene carbonate：Three fluoropropylene carbonates：
The volume ratio of hydrofluoroether is 2：6：3, lithium hexafluoro phosphate molar concentration is 0.8mol/L, and di-oxalate lithium borate molar concentration is
0.2mol/L, the addition of propylene sulfite is 1%.
Embodiment 5
By fluorinated ethylene carbonate, three fluoropropylene carbonates, hydrofluoroether, lithium hexafluoro phosphate, di-oxalate lithium borate and Asia
Sulfuric acid propylene, which is uniformly mixed according to a ratio, produces high-voltage electrolyte, wherein, fluorinated ethylene carbonate：Three fluoropropylene carbonates：
The volume ratio of hydrofluoroether is 3：6：1, lithium hexafluoro phosphate molar concentration is 0.9mol/L, and di-oxalate lithium borate molar concentration is
0.1mol/L, the addition of propylene sulfite is 2%.
Embodiment 6
By fluorinated ethylene carbonate, three fluoropropylene carbonates, hydrofluoroether, lithium hexafluoro phosphate, di-oxalate lithium borate and Asia
Sulfuric acid propylene, which is uniformly mixed according to a ratio, produces high-voltage electrolyte, wherein, fluorinated ethylene carbonate：Three fluoropropylene carbonates：
The volume ratio of hydrofluoroether is 2：7：1, lithium hexafluoro phosphate molar concentration is 1.1mol/L, and di-oxalate lithium borate molar concentration is
0.1mol/L, the addition of propylene sulfite is 1.2%.
Comparative example
With conventional LiPF6/ EC+DMC+EMC electrolyte systems as a comparison case, by lithium hexafluoro phosphate（LiPF6）, carbonic acid
Vinyl acetate（EC）, dimethyl carbonate（DMC）, methyl ethyl carbonate（EMC）And propylene sulfite is uniformly mixed according to a ratio and produced often
Electrolyte is advised, wherein, ethylene carbonate：Dimethyl carbonate：The volume ratio of methyl ethyl carbonate is 3：2：5, LiPF6Molar concentration
For 1.2 mol/L, the addition of propylene sulfite is 2%.
Using linear sweep voltammetry (LSV) to the high-voltage electrolyte of the embodiment of the present invention 1 and the conventional electrolysis of comparative example
The electrochemical window of liquid is tested, and test condition is as follows：Working electrode：Platinum filament；To electrode：Platinized platinum；Reference electrode：Lithium piece；
Sweep speed：1mV/sec；25 DEG C of normal temperature, obtained LSV curve comparison figures are as shown in figure 1, the height of other each embodiments of the invention
Press electrolyte similar with Fig. 1 with the LSV curve comparison figures of conventional electrolysis liquid gained under the conditions of same test of comparative example, therefore
Do not enumerate one by one.
As can be seen from Figure 1：Oxidation reaction takes place in voltage 5.0V in the conventional electrolysis liquid of comparative example, and 5.3V is left
It is right obvious oxidation peak occur；And the high-voltage electrolyte of embodiment 1 is not until voltage 6.0V occurs obvious oxidation reaction；Explanation
Relatively conventional electrolyte, high-voltage electrolyte of the invention has more preferable resistance to oxidation, high pressure resistant property.
Embodiment described above is a kind of preferably scheme of the present invention, not makees any formal to the present invention
Limitation, also has other variants and remodeling on the premise of without departing from the technical scheme described in claim.
Claims (1)
1. a kind of high voltage electrolyte of lithium ion battery, it is characterised in that the high-voltage electrolyte is by organic solvent, electrolyte lithium salt
And cathode film formation additive composition, wherein, organic solvent is fluorinated ethylene carbonate, three fluoropropylene carbonates and hydrofluoroether group
Into mixed solvent, the electrolyte lithium salt is the mixing lithium salts that lithium hexafluoro phosphate and di-oxalate lithium borate are constituted, organic solvent
In, fluorinated ethylene carbonate：Three fluoropropylene carbonates：The volume ratio of hydrofluoroether is 2 ~ 3：4~7：1 ~ 3, in high-voltage electrolyte,
The lithium hexafluoro phosphate molar concentration is 0.8 ~ 1.2mol/L, and the di-oxalate lithium borate molar concentration is 0.1 ~ 0.2mol/L,
On the basis of high-voltage electrolyte gross mass, the addition of cathode film formation additive is 1 ~ 2%, and the cathode film formation additive is Asia
Sulfuric acid propylene.
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| CN201310276370.3A CN104282939B (en) | 2013-07-02 | 2013-07-02 | A kind of high voltage electrolyte of lithium ion battery |
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| CN104282939A CN104282939A (en) | 2015-01-14 |
| CN104282939B true CN104282939B (en) | 2017-08-29 |
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| CN109713367B (en) * | 2018-12-28 | 2022-02-22 | 安普瑞斯（南京）有限公司 | Silicon-containing high-energy-density lithium ion battery |
| CN111129576A (en) * | 2019-12-20 | 2020-05-08 | 山东精工电子科技有限公司 | High-temperature-resistant long-cycle lithium ion battery |
| CN111244542A (en) * | 2020-03-21 | 2020-06-05 | 湖州安和材料科技有限公司 | Low-temperature-resistant lithium battery electrolyte and preparation process thereof |
| CN114530631A (en) * | 2020-11-23 | 2022-05-24 | 天津大学 | Application of electrolyte additive in improving battery electrolyte adding performance |
| CN113782835B (en) * | 2021-08-27 | 2023-07-04 | 华中科技大学 | Perfluorinated solvent high-voltage electrolyte and application thereof in lithium ion battery |
| CN114725509A (en) * | 2022-04-25 | 2022-07-08 | 西安交通大学 | Sulfone-based lithium battery electrolyte and lithium battery |
| CN114976239A (en) * | 2022-05-31 | 2022-08-30 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | High-safety lithium ion battery electrolyte suitable for full sea depth |
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