CN106972197A - A kind of anti-overcharge lithium battery electrolytes and preparation method thereof - Google Patents
A kind of anti-overcharge lithium battery electrolytes and preparation method thereof Download PDFInfo
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- CN106972197A CN106972197A CN201710293086.5A CN201710293086A CN106972197A CN 106972197 A CN106972197 A CN 106972197A CN 201710293086 A CN201710293086 A CN 201710293086A CN 106972197 A CN106972197 A CN 106972197A
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- lithium
- overcharge
- lithium battery
- carbonate
- battery electrolytes
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 65
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000003792 electrolyte Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 34
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 34
- 239000000654 additive Substances 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 16
- -1 esters compound Chemical class 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 11
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical class C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 150000003871 sulfonates Chemical class 0.000 claims abstract description 7
- 239000003660 carbonate based solvent Substances 0.000 claims abstract description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 36
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 13
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 12
- 235000010338 boric acid Nutrition 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 229960002645 boric acid Drugs 0.000 claims description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 12
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 12
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 8
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 7
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical group CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- QRMHDYCPNIVCBO-UHFFFAOYSA-N [SH2]=N.[F] Chemical compound [SH2]=N.[F] QRMHDYCPNIVCBO-UHFFFAOYSA-N 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
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 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 1
- 239000000126 substance Substances 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- IDGCBXSROJHVOG-UHFFFAOYSA-N [Li].[SH2]=N.[F] Chemical compound [Li].[SH2]=N.[F] IDGCBXSROJHVOG-UHFFFAOYSA-N 0.000 description 10
- 238000005352 clarification Methods 0.000 description 10
- 239000011261 inert gas Substances 0.000 description 10
- 230000002045 lasting effect Effects 0.000 description 10
- 238000004806 packaging method and process Methods 0.000 description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000001294 propane Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000001467 acupuncture Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RTZKMGZSJBRJFI-UHFFFAOYSA-N boric acid;lithium Chemical compound [Li].OB(O)O RTZKMGZSJBRJFI-UHFFFAOYSA-N 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000007634 remodeling Methods 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
-
- 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)
- 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 anti-overcharge lithium battery electrolytes and preparation method thereof, belong to lithium battery material technical field.The present invention is made up of lithium salts, double solvents and additive；It is characterized in that：The lithium salts is at least one of inorganic lithium salt, organic boronic lithium, lithium salts of sulfonimide；The double solvents is at least two solvents in carbonate-based solvent；The additive is at least one of sulfurous esters compound, carbonats compound, sulfonates compounds and the DfBP of 2', 4' dimethyl 2,4；The quality of the additive accounts for 1% the 15% of electrolyte.The present invention prepares anti-overcharge lithium battery electrolytes, and oxidation Decomposition can occur when lithium battery is overcharged prior to electrolyte, and contact of the cut-off electrolyte with electrode surface lifts security performance.
Description
Technical field
The present invention relates to lithium battery material technical field, more particularly to a kind of anti-overcharge lithium battery electrolytes and its preparation side
Method.
Background technology
Lithium ion battery is current specific energy highest rechargeable battery, and it instead of lithium metal with the compound of embedding lithium and makees
For anode, so that passivation and the Li dendrite problem of traditional lithium battery Anodic are overcome, and also lithium ion battery has work electricity
The advantages of pressure is high, energy density is high, power density is big, has been widely used in the fields such as number, mobile communication, and progressively in state
Anti-, military aspect application, in recent years, with developing rapidly for electric bicycle and electric automobile, lithium ion battery is considered as
It is the Vehicular dynamic battery of current most potential development.But the electrolyte that most lithium batteries are used at present is inflammable carbonic ester
Mixed solvent system, if lithium cell charging is incorrect when causing to overcharge, the current potential of electrode is higher, easily triggers solvent
Decomposition reaction, raises the temperature of battery, triggers battery core rupture, burning or blast to cause safety problem, restriction lithium battery to
The bottleneck that maximization, energetic direction are developed.
For this problem, researchers are constituted by optimizing electrolyte, a small amount of functional mass are introduced, in inside battery
Set up a kind of anti-overcharge electrochemistry self-protective mechanism.As United States Patent (USP) US5776627 discloses a kind of anti-overcharge additive
Biphenyl, when over-charging of battery, aerogenesis additive biphenyl will be aggregated in electrode surface formation SEI films, prevent the migration of lithium ion,
The internal resistance of cell is improved, it is powered off and then improves the security performance of battery, but this kind of additive gas production is more, easily triggers electricity
Core explosion causes security incident.Therefore, a kind of suitable overcharge protection additives are found, SEI films had both been avoided that to overcharge and is caused
Safety problem, be unlikely to influence battery charging and discharging performance again, be the current technical problem for being badly in need of solving.
The content of the invention
In order to make up the deficiencies in the prior art, the invention provides a kind of anti-overcharge lithium battery electrolytes and its preparation side
Method.
The technical scheme is that：
A kind of anti-overcharge lithium battery electrolytes, are made up of lithium salts, double solvents and additive；The lithium salts is inorganic lithium salt, had
At least one of machine lithium borate, lithium salts of sulfonimide；The double solvents is molten at least two in carbonate-based solvent
Agent；The additive be at least one of sulfurous esters compound, carbonats compound, sulfonates compounds and
2', 4'- dimethyl -2,4- DfBPs；The quality of the additive accounts for the 1%-15% of electrolyte.
Preferably, the concentration of the inorganic lithium salt is 0.5-2mol/L, the concentration of the lithium salts of sulfonimide
For 0.1-0.5mol/L, the concentration of the organic boronic lithium is 0.1-0.5mol/L.
Preferably, the inorganic lithium salt is LiPF6Or LiBF4；Described organic boronic lithium is dioxalic acid boric acid
Lithium, difluorine oxalic acid boracic acid lithium, described lithium salts of sulfonimide are double trifluoromethanesulfonimide lithiums, double fluorine sulfimide lithiums.
Preferably, the carbonate-based solvent is made up of cyclic carbonate and linear carbonates.
Further, the cyclic carbonate is ethylene carbonate and/or propene carbonate.
Preferably, the linear carbonates are one kind in diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate
Or it is a variety of.
Preferably, cyclic carbonate and the mass ratio of linear carbonates are 1:1-4.
Preferably, the sulfurous esters compound is ethylene sulfite, propylene sulfite；The carbonic acid
Ester type compound is vinylene carbonate and/or fluorinated ethylene carbonate；The sulfonates compounds are in 1,3- propane sulphurs
Fat.
Further, the additive is carbonats compound, sulfonates compounds and 2', 4'- dimethyl -2,4-
The mixture of DfBP.
The preparation method of the anti-overcharge lithium battery electrolytes, including step：
1）Take solvent and be well mixed, be cooled to less than 10 DEG C；
2）Lithium salts is added under conditions of temperature is not higher than 10 DEG C, and is stirred to lithium salts dissolving；
3）Additive is added, continues to stir to uniform solution is formed, obtains the anti-overcharge lithium battery electrolytes.
The lithium battery electrolytes that overcharge meet following require：Impurity≤0.1% (GC), moisture≤15ppm, heavy metal≤
1ppm, chloride≤1ppm, sulfate≤5ppm, color≤50APHA；Other metal impurities Na, K, Fe, K, Mg etc.≤1ppm.
Beneficial effects of the present invention are：
Compared with prior art, beneficial effects of the present invention are：
When the 1st, overcharging, preferential other components react, and gas production is less, can effectively prevent lithium battery from overcharging caused
The generation of the safety problems such as fire, blast, adds the security of battery；
2nd, smaller to the Conductivity of electrolyte, charge and discharge efficiency high can meet 500 charge and discharge requirements more than 85%, especially
The high temperature cyclic performance of lithium battery can be improved；
3rd, strong applicability, available for a variety of lithium electrochemical cells systems such as system such as graphite/cobalt acid lithium, graphite/LiMn2O4.
The anti-overcharge lithium battery electrolytes of the present invention, in the case where not influenceing the behavior patterns such as capacity, the cycle performance of lithium battery
Effectively prevent lithium battery overcharge cause it is on fire, blast etc. safety problem generation, greatly promote lithium battery security performance, widen
Its scope of application, available for a variety of lithium electrochemical cells systems.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, without having to pay creative labor, may be used also
To obtain other accompanying drawings according to these accompanying drawings.
Fig. 1 is to use embodiment 1（Blank）With the electrochemistry cyclic voltammogram of electrolyte made from embodiment 4.
Embodiment
Embodiment 1：
By dimethyl carbonate（DMC）, methyl ethyl carbonate（EMC）, ethylene carbonate（EC）According to mass ratio 1:1:1 sequentially adds,
When temperature is down to 10 DEG C, lithium salts is slowly added in the case of ensureing that temperature is not higher than 10 DEG C, preparing hexafluorophosphoric acid lithium concentration is
1mol/L, difluorine oxalic acid boracic acid lithium are the electrolyte that 0.2mol/L, double fluorine sulfimide lithium concentrations are 0.1mol/L, lasting stirring
Until solution clarification, is then sufficiently stirred for, it is transferred to and stores stand-by full of inert gas Packaging Bottle.
Embodiment 2：
By dimethyl carbonate（DMC）, methyl ethyl carbonate（EMC）, ethylene carbonate（EC）According to mass ratio 1:1:1 sequentially adds,
When temperature is down to 10 DEG C, lithium salts is slowly added in the case of ensureing that temperature is not higher than 10 DEG C, preparing hexafluorophosphoric acid lithium concentration is
1mol/L, difluorine oxalic acid boracic acid lithium are the electrolyte that 0.2mol/L, double fluorine sulfimide lithium concentrations are 0.1mol/L, lasting stirring
Until solution clarification；Then 1% vinylene carbonate of addition, 2% 1 are calculated according to electrolyte gross mass, 3- propane sultones, and
After be sufficiently stirred for, be transferred to full of inert gas Packaging Bottle store it is stand-by.
Embodiment 3：
By dimethyl carbonate（DMC）, methyl ethyl carbonate（EMC）, ethylene carbonate（EC）According to mass ratio 1:1:1 sequentially adds,
When temperature is down to 10 DEG C, lithium salts is slowly added in the case of ensureing that temperature is not higher than 10 DEG C, preparing hexafluorophosphoric acid lithium concentration is
1mol/L, difluorine oxalic acid boracic acid lithium are the electrolyte that 0.2mol/L, double fluorine sulfimide lithium concentrations are 0.1mol/L, lasting stirring
Until solution clarification；Addition 2% 1 then is calculated according to electrolyte gross mass, 3- propane sultones are then sufficiently stirred for, are transferred to
Store stand-by full of inert gas Packaging Bottle.
Embodiment 4：
By dimethyl carbonate（DMC）, methyl ethyl carbonate（EMC）, ethylene carbonate（EC）According to mass ratio 1:1:1 sequentially adds,
When temperature is down to 10 DEG C, lithium salts is slowly added in the case of ensureing that temperature is not higher than 10 DEG C, preparing hexafluorophosphoric acid lithium concentration is
1mol/L, difluorine oxalic acid boracic acid lithium are the electrolyte that 0.2mol/L, double fluorine sulfimide lithium concentrations are 0.1mol/L, lasting stirring
Until solution clarification；2% anti-over-charging 2', 4'- dimethyl -2,4- DfBP of addition then is calculated according to electrolyte gross mass,
Then it is sufficiently stirred for, is transferred to and stores stand-by full of inert gas Packaging Bottle.
Embodiment 5：
By dimethyl carbonate（DMC）, methyl ethyl carbonate（EMC）, ethylene carbonate（EC）According to mass ratio 1:1:1 sequentially adds,
When temperature is down to 10 DEG C, lithium salts is slowly added in the case of ensureing that temperature is not higher than 10 DEG C, preparing hexafluorophosphoric acid lithium concentration is
1mol/L, difluorine oxalic acid boracic acid lithium are the electrolyte that 0.2mol/L, double fluorine sulfimide lithium concentrations are 0.1mol/L, lasting stirring
Until solution clarification；Then 1% vinylene carbonate of addition, 2% 1 are calculated according to electrolyte gross mass, 3- propane sultones, and
After be sufficiently stirred for, be transferred to full of inert gas Packaging Bottle store it is stand-by.
Embodiment 6：
By dimethyl carbonate（DMC）, methyl ethyl carbonate（EMC）, ethylene carbonate（EC）According to mass ratio 1:1:1 sequentially adds,
When temperature is down to 10 DEG C, lithium salts is slowly added in the case of ensureing that temperature is not higher than 10 DEG C, preparing hexafluorophosphoric acid lithium concentration is
1mol/L, difluorine oxalic acid boracic acid lithium are the electrolyte that 0.2mol/L, double fluorine sulfimide lithium concentrations are 0.1mol/L, lasting stirring
Until solution clarification；Then 1% vinylene carbonate of addition, 2% anti-over-charging 2', 4'- diformazan are calculated according to electrolyte gross mass
Base -2,4- DfBP, is then sufficiently stirred for, and is transferred to and stores stand-by full of inert gas Packaging Bottle.
Embodiment 7：
By dimethyl carbonate（DMC）, methyl ethyl carbonate（EMC）, ethylene carbonate（EC）According to mass ratio 1:1:1 sequentially adds,
When temperature is down to 10 DEG C, lithium salts is slowly added in the case of ensureing that temperature is not higher than 10 DEG C, preparing hexafluorophosphoric acid lithium concentration is
1mol/L, difluorine oxalic acid boracic acid lithium are the electrolyte that 0.2mol/L, double fluorine sulfimide lithium concentrations are 0.1mol/L, lasting stirring
Until solution clarification；Then 2% 1,3- propane sultones of addition, 2% anti-over-charging 2', 4'- bis- are calculated according to electrolyte gross mass
Methyl -2,4- DfBP, is then sufficiently stirred for, and is transferred to and stores stand-by full of inert gas Packaging Bottle.
Embodiment 8：
By dimethyl carbonate（DMC）, methyl ethyl carbonate（EMC）, ethylene carbonate（EC）According to mass ratio 1:1:1 sequentially adds,
When temperature is down to 10 DEG C, lithium salts is slowly added in the case of ensureing that temperature is not higher than 10 DEG C, preparing hexafluorophosphoric acid lithium concentration is
1mol/L, difluorine oxalic acid boracic acid lithium are the electrolyte that 0.2mol/L, double fluorine sulfimide lithium concentrations are 0.1mol/L, lasting stirring
Until solution clarification；Then 1% vinylene carbonate of addition, 2% 1,3- propane sultones, 2% are calculated according to electrolyte gross mass
Anti-over-charging 2', 4'- dimethyl -2,4- DfBP, is then sufficiently stirred for, and is transferred to and stores stand-by full of inert gas Packaging Bottle.
Embodiment 9：
By dimethyl carbonate（DMC）, methyl ethyl carbonate（EMC）, ethylene carbonate（EC）According to mass ratio 1:1:1 sequentially adds,
When temperature is down to 10 DEG C, lithium salts is slowly added in the case of ensureing that temperature is not higher than 10 DEG C, preparing hexafluorophosphoric acid lithium concentration is
1mol/L, difluorine oxalic acid boracic acid lithium are the electrolyte that 0.2mol/L, double fluorine sulfimide lithium concentrations are 0.1mol/L, lasting stirring
Until solution clarification；Then 1% vinylene carbonate of addition, 2% 1,3- propane sultones, 3% are calculated according to electrolyte gross mass
Anti-over-charging 2', 4'- dimethyl -2,4- DfBP, is then sufficiently stirred for, and is transferred to and stores stand-by full of inert gas Packaging Bottle.
Embodiment 10：
By dimethyl carbonate（DMC）, methyl ethyl carbonate（EMC）, ethylene carbonate（EC）According to mass ratio 1:1:1 sequentially adds,
When temperature is down to 10 DEG C, lithium salts is slowly added in the case of ensureing that temperature is not higher than 10 DEG C, preparing hexafluorophosphoric acid lithium concentration is
1mol/L, difluorine oxalic acid boracic acid lithium are the electrolyte that 0.2mol/L, double fluorine sulfimide lithium concentrations are 0.1mol/L, lasting stirring
Until solution clarification；Then 1% vinylene carbonate of addition, 2% 1,3- propane sultones, 5% are calculated according to electrolyte gross mass
Anti-over-charging 2', 4'- dimethyl -2,4- DfBP, is then sufficiently stirred for, and is transferred to and stores stand-by full of inert gas Packaging Bottle.
Electrolyte in above-mentioned 10 embodiments is subjected to conductive capability test, data are shown in Table 1.As seen from Table 1, this hair
It is bright to prepare anti-overcharge lithium battery electrolytes, it there is no influence for the conductive capability of electrolyte.
In addition, cyclic voltammetry has been carried out for embodiment 1 and embodiment 4, by open-circuit voltage forward scan to 5.5V,
It is 1mv/s to sweep speed, and then flyback to 3.0V, data are shown in Fig. 1.As seen from Figure 1, the present invention prepares anti-overcharge lithium battery electrolysis
Oxidation Decomposition, contact of the cut-off electrolyte with electrode surface, lifting can occur when lithium battery is overcharged prior to electrolyte for liquid
Security performance.
In addition, being filled into soft-package battery of the design capacity for 2Ah respectively to the electrolyte of above-mentioned 10 embodiments with 1C times
Rate, which is crossed, is charged to 6.3V, and the test such as acupuncture, short circuit has been carried out afterwards, and test result is shown in Table 2.As seen from Table 2, the present invention prepares anti-
Lithium battery security performance can be greatly promoted by overcharging lithium battery electrolytes.
Finally, the soft-package battery that design capacity is 2Ah is filled into respectively to the electrolyte of above-mentioned 10 embodiments, carries out 55
DEG C tested with 1C multiplying powers charge and discharge 500 weeks, test result such as table 3.The present invention prepares anti-overcharge lithium battery as can be seen from Table 3
Solution liquid energy enough improves lithium battery cycle performance, lifts the service life of lithium battery.
Table 1
Table 2
Table 3
The above described is only a preferred embodiment of the present invention, be not the limitation for making other forms to the present invention, it is any ripe
Know the equivalent reality that professional and technical personnel was changed or be modified as equivalent variations possibly also with the technology contents of the disclosure above
Example is applied applied to other fields, but every without departing from technical solution of the present invention content, according to the present invention technical spirit to
Any simple modification, equivalent variations and remodeling that upper embodiment is made, still fall within the protection domain of technical solution of the present invention.
Claims (10)
1. a kind of anti-overcharge lithium battery electrolytes, are made up of lithium salts, double solvents and additive；It is characterized in that：The lithium salts
For at least one of inorganic lithium salt, organic boronic lithium, lithium salts of sulfonimide；The double solvents is in carbonate-based solvent
At least two solvents；The additive is in sulfurous esters compound, carbonats compound, sulfonates compounds
At least one and 2', 4'- dimethyl -2,4- DfBPs；The quality of the additive accounts for the 1%-15% of electrolyte.
2. anti-overcharge lithium battery electrolytes as claimed in claim 1, it is characterised in that：The concentration of the inorganic lithium salt is 0.5-
2mol/L, the concentration of the lithium salts of sulfonimide is 0.1-0.5mol/L, and the concentration of the organic boronic lithium is 0.1-
0.5mol/L。
3. anti-overcharge lithium battery electrolytes as claimed in claim 1 or 2, it is characterised in that：The inorganic lithium salt is LiPF6Or
LiBF4；Described organic boronic lithium is dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium, and described lithium salts of sulfonimide is double
Trifluoromethanesulfonimide lithium, double fluorine sulfimide lithiums.
4. anti-overcharge lithium battery electrolytes as claimed in claim 1 or 2, it is characterised in that：The carbonate-based solvent is by ring-type
Carbonic ester and linear carbonates composition.
5. anti-overcharge lithium battery electrolytes as claimed in claim 4, it is characterised in that：The cyclic carbonate is ethylene carbonate
And/or propene carbonate.
6. anti-overcharge lithium battery electrolytes as claimed in claim 4, it is characterised in that：The linear carbonates are carbonic acid diethyl
One or more in ester, dimethyl carbonate, methyl ethyl carbonate.
7. anti-overcharge lithium battery electrolytes as claimed in claim 4, it is characterised in that：The matter of cyclic carbonate and linear carbonates
Amount is than being 1:1-4.
8. anti-overcharge lithium battery electrolytes as claimed in claim 1 or 2, it is characterised in that：The sulfurous esters compound is
Ethylene sulfite, propylene sulfite；The carbonats compound is vinylene carbonate and/or fluoro ethylene carbonate
Ester；The sulfonates compounds are 1,3- propane sulphur lactones.
9. anti-overcharge lithium battery electrolytes as claimed in claim 8, it is characterised in that：The additive is carbonates chemical combination
The mixture of thing, sulfonates compounds and 2', 4'- dimethyl -2,4- DfBPs.
10. the preparation method of anti-overcharge lithium battery electrolytes as claimed in claim 1, it is characterised in that including step：
1）Take solvent and be well mixed, be cooled to less than 10 DEG C；
2）Lithium salts is added under conditions of temperature is not higher than 10 DEG C, and is stirred to lithium salts dissolving；
3）Additive is added, continues to stir to uniform solution is formed, obtains the anti-overcharge lithium battery electrolytes.
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| CN108134133A (en) * | 2017-11-30 | 2018-06-08 | 深圳市沃特玛电池有限公司 | A kind of lithium battery electrolytes and preparation method thereof |
| CN108428920A (en) * | 2018-03-30 | 2018-08-21 | 王敏 | A kind of preparation method of high temperature resistant type electrolyte |
| CN113054253A (en) * | 2019-12-29 | 2021-06-29 | 江西格林德能源有限公司 | Overcharge-proof electrolyte of lithium ion battery |
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| CN106252725A (en) * | 2016-08-31 | 2016-12-21 | 天津市捷威动力工业有限公司 | A kind of Overcharge prevention electrolyte based on ternary lithium ion battery and lithium ion battery |
| CN106450462A (en) * | 2016-12-27 | 2017-02-22 | 石家庄圣泰化工有限公司 | Electrolyte of high-voltage wide-temperature-range lithium-ion battery |
| CN106532117A (en) * | 2016-11-17 | 2017-03-22 | 张家港市国泰华荣化工新材料有限公司 | Lithium ion battery electrolyte and lithium ion battery |
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| CN106252725A (en) * | 2016-08-31 | 2016-12-21 | 天津市捷威动力工业有限公司 | A kind of Overcharge prevention electrolyte based on ternary lithium ion battery and lithium ion battery |
| CN106532117A (en) * | 2016-11-17 | 2017-03-22 | 张家港市国泰华荣化工新材料有限公司 | Lithium ion battery electrolyte and lithium ion battery |
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| CN108134133A (en) * | 2017-11-30 | 2018-06-08 | 深圳市沃特玛电池有限公司 | A kind of lithium battery electrolytes and preparation method thereof |
| CN108428920A (en) * | 2018-03-30 | 2018-08-21 | 王敏 | A kind of preparation method of high temperature resistant type electrolyte |
| CN113054253A (en) * | 2019-12-29 | 2021-06-29 | 江西格林德能源有限公司 | Overcharge-proof electrolyte of lithium ion battery |
| CN113054253B (en) * | 2019-12-29 | 2022-08-12 | 江西格林德能源有限公司 | Overcharge-proof electrolyte of lithium ion battery |
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