CN106025338A - Electrolyte for rechargeable micro lithium battery - Google Patents
Electrolyte for rechargeable micro lithium battery Download PDFInfo
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- CN106025338A CN106025338A CN201610400478.2A CN201610400478A CN106025338A CN 106025338 A CN106025338 A CN 106025338A CN 201610400478 A CN201610400478 A CN 201610400478A CN 106025338 A CN106025338 A CN 106025338A
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- Prior art keywords
- electrolyte
- additive
- lithium battery
- volume ratio
- vitamin
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 132
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 50
- 230000000996 additive effect Effects 0.000 claims abstract description 48
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 36
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 30
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 19
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 19
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229930003268 Vitamin C Natural products 0.000 claims abstract description 18
- 235000019154 vitamin C Nutrition 0.000 claims abstract description 18
- 239000011718 vitamin C Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical group C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 claims description 20
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 17
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 8
- 241001597008 Nomeidae Species 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 11
- 238000002485 combustion reaction Methods 0.000 abstract description 8
- 239000003063 flame retardant Substances 0.000 abstract description 6
- 229910013075 LiBF Inorganic materials 0.000 abstract description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract 2
- 239000002131 composite material Substances 0.000 abstract 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 229930003231 vitamin Natural products 0.000 description 3
- 235000013343 vitamin Nutrition 0.000 description 3
- 239000011782 vitamin Substances 0.000 description 3
- 229940088594 vitamin Drugs 0.000 description 3
- 150000003722 vitamin derivatives Chemical class 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000007785 strong electrolyte Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000003660 carbonate based solvent Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- NHWZQIYTQZEOSJ-UHFFFAOYSA-N carbonic acid;phosphoric acid Chemical compound OC(O)=O.OP(O)(O)=O NHWZQIYTQZEOSJ-UHFFFAOYSA-N 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002459 sustained effect Effects 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
-
- 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
-
- 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
-
- 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)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to an electrolyte, and particularly to a flame-retardant and low-temperature-resistant electrolyte for a rechargeable micro lithium battery. The electrolyte comprises an electrolyte lithium salt, a non-aqueous organic solvent and a first additive, wherein the non-aqueous organic solvent comprises propylene carbonate and triethyl phosphate at the volume ratio of 65-80 to 20-35; the first additive is a composite additive which comprises vitamin C and ethylene carbonate at the volume ratio of 1-4 to 2-5; and the electrolyte lithium salt comprises LiBF<4> and Li<3>PO<4> at the mass ratio of 8-12 to 1. The lithium ion battery electrolyte provided by the invention has the low-temperature-resistant and flame-retardant characteristics; the electrolyte is applicable to a rechargeable lithium battery or a lithium ion micro battery with the temperature lower limit of minus 40 DEG C; and meanwhile, the battery is endowed with a certain combustion resistance characteristic.
Description
Technical field
The present invention relates to a kind of electrolyte, particularly relate to a kind of fire-retardant, low temperature resistant filled miniature lithium battery electrolyte.
Background technology
Micro-energy refer to the three-dimensional dimension at least bidimensional of power supply less than 1 millimeter, maximum one-dimensional be not more than 1 centimetre micro-
Type power supply, typical size 1mm*1mm*10mm is the least.It is mainly used in microsensor, no worker monitor Full-automatic monitoring
Instrument, miniature implantable medical devices etc..Directly on surface-mounted integrated circuit, integrated micro-energy is following development inexorable trend.
Micro-energy battery candidate mainly includes metal-air battery, Ni-MH battery and lithium ion battery, solaode.
In very small chemical power supply system, need mainly positive pole, negative pole and the machinability of electrolyte and the safety considered, for
Lithium battery, safety issue relates generally to combustibility；If it is considered that by the left unguarded instrument application of integrated micro battery to outlying
If unmanned area, it is contemplated that the environment in these areas, generally, this kind of area is all not suitable for people and lives for a long time
Place, typically has the high and cold or dry hot feature of anhydrous height.
Common lithium-ion battery electrolytes system, is made up of with lithium hexafluoro phosphate carbonate-based solvent, carbonates
Solvent, such as ethylene carbonate, Allyl carbonate, dimethyl carbonate etc., has inflammable feature.The chemical stability of lithium hexafluoro phosphate
The most sufficient, the HF of generation has the strongest corrosivity.
Summary of the invention
It is an object of the invention to provide a kind of fire-retardant, low temperature resistant filled miniature lithium battery electrolyte.
The above-mentioned technical purpose of the present invention has the technical scheme that
One can fill miniature lithium battery electrolyte, and it includes electrolyte lithium salt, non-aqueous organic solvent and the first additive；
Described non-aqueous organic solvent is Allyl carbonate and triethyl phosphate；The volume ratio of Allyl carbonate and triethyl phosphate is
65-80:20-35；
Described first additive is vitamin C and the compound additive of ethylene carbonate composition；Vitamin C and ethylene carbonate
Volume ratio is 1-4:2-5；
Described electrolyte lithium salt is LiBF4And Li3PO4, LiBF4And Li3PO4Mass ratio be 8-12:1.
The Main Function of non-aqueous organic solvent Allyl carbonate PC of the present invention and triethyl phosphate TEP is to ensure that electrolyte has
There is the relatively low freezing point of ratio, and give the resistance to combustion ability that electrolyte is the strongest simultaneously；The present invention the first additive vitamin V C and
The Main Function of ethylene carbonate EC mixture is the compatibility strengthening electrolyte and Carbon anode, and strengthen simultaneously electrolyte and
The interface stability of negative pole；Electrolyte lithium salt LiBF of the present invention4And Li3PO4Main Function be to improve ionic conductivity, and
And improve the stability at electrolyte and both positive and negative polarity interface, improve the flame-retarding characteristic of electrolyte simultaneously.Therefore, the lithium ion of the present invention
Battery electrolyte, has low temperature resistant, fire-retardant feature, be suitable for lowest temperature to-40 degree low temperature under use filled lithiums or
Lithium ion micro battery, gives the flame resistant characteristic that battery is certain simultaneously.
As preferably, described electrolyte lithium salt LiBF4Concentration is 0.05-0.25mol/L, Li3PO4Concentration be 0.008-
0.02mol/L。
Described electrolyte lithium salt LiBF4Concentration refers to LiBF4Concentration in can filling miniature lithium battery electrolyte；Described electricity
Solve matter lithium salts Li3PO4Concentration refers to Li3PO4Concentration in can filling miniature lithium battery electrolyte.Electrolyte lithium salt LiBF4With
Li3PO4Certain concentration range can increase the ionic conductivity of electrolyte, improve the stability of electrolyte and both positive and negative polarity interface,
Improve the flame-retarding characteristic of electrolyte simultaneously.
As preferably, described electrolyte lithium salt LiBF4Concentration is 0.1mol/L, Li3PO4Concentration be 0.01mol/L.
Inventor finds, this electrolyte lithium salt LiBF4And Li3PO4Certain concentration to the ionic conductivity of electrolyte, electricity
Solve liquid and improve optimal with the flame-retarding characteristic of the stability at both positive and negative polarity interface and electrolyte.
As preferably, the volume ratio of described Allyl carbonate, triethyl phosphate, vitamin C and ethylene carbonate is 65-
80:20-35:1-4:2-5.
Non-aqueous organic solvent Allyl carbonate PC of special ratios scope, triethyl phosphate TEP, the first additive vitamin
The freezing point that can reduce electrolyte further of VC and ethylene carbonate EC, give the strongest resistance to combustion ability of electrolyte, increase simultaneously
The compatibility of strong electrolyte and Carbon anode and electrolyte and the interface stability of negative pole.
As preferably, the volume ratio of described Allyl carbonate, triethyl phosphate, vitamin C and ethylene carbonate is 70:
25:2:3.
Inventor finds, non-aqueous organic solvent Allyl carbonate PC of this special ratios, triethyl phosphate TEP, first adds
Add agent vitamin V C and ethylene carbonate EC to reduce electrolyte freezing point, give the strongest resistance to combustion ability of electrolyte, with
The best results of the interface stability of Shi Zengqiang electrolyte and the compatibility of Carbon anode and electrolyte and negative pole.
As preferably, described Allyl carbonate, the volume ratio of triethyl phosphate are 68-75:20-30.
Non-aqueous organic solvent Allyl carbonate PC of special ratios scope, triethyl phosphate TEP can reduce electricity further
Solve the freezing point of liquid, and give the resistance to combustion ability that electrolyte is the strongest simultaneously.
As preferably, the volume ratio of described vitamin C and ethylene carbonate is 1-3:2-4.
First additive of special ratios scope can further enhance the compatibility of electrolyte and Carbon anode, and increase simultaneously
Strong electrolyte and the interface stability of negative pole.
As preferably, also including Second addition in electrolyte, described Second addition is the interpolation that structural formula 1 represents
Agent:
[structural formula 1]
Wherein, R is CH3、C2H3、C6H6Alkyl and derivant thereof or C5H5N nitrogen heterocyclic ring aryl and derivant thereof.
The material of this structure of Second addition coordinates other composition in electrolyte especially to coordinate the first additive, permissible
Make electrolyte of the present invention in a low temperature of-40 DEG C, all can carry out heavy-current discharge；Ensure that electrolyte has than relatively low solidification
Point, and give the resistance to combustion ability that electrolyte is the strongest simultaneously.
As preferably, the quality of the quality of described Second addition and described non-aqueous organic solvent is 0.1-than scope
0.4%。
As preferably, electrolyte also including, the 3rd additive, described 3rd additive are oxolane and 2-methyl four
One or both in hydrogen furan.
When 3rd additive is one or both in oxolane (THF) and 2-methyltetrahydrofuran (2Me-THF) more
Be conducive to the compatibility strengthening electrolyte with Carbon anode, and strengthen electrolyte and the interface stability of negative pole simultaneously.
As preferably, the quality of described 3rd additive and the quality of described non-aqueous organic solvent are 0.1-than span
0.4%.This span studies for a long period of time gained through inventor, is conducive to playing the 3rd additive to lithium-ion electrolyte low
Under the conditions of temperature and the interface stability of negative pole.
As preferably, also including the 4th additive in electrolyte, described 4th additive is vinylene carbonate, propylene
One or many in nitrile, dimethyl sulfite, 1,3-propane sultone, fluorinated ethylene carbonate and trimethoxy boroxane
Kind.
4th additive coordinates other composition in electrolyte especially to coordinate the first additive, Second addition or/and the
Three additives, can improve ionic conductivity, and improve the stability of electrolyte and both positive and negative polarity interface, improve electrolyte simultaneously
Flame-retarding characteristic.
As preferably, the quality of described 4th additive and the quality of described non-aqueous organic solvent are 0.1-than span
0.4%。
As preferably, also including the 5th additive in electrolyte, the 5th additive is the additive that structural formula 2 represents:
[structural formula 2].
The material of this structure of the present invention coordinates other composition in electrolyte especially to coordinate the first additive, can make this
Invention electrolyte, in a low temperature of-40 DEG C, all can carry out heavy-current discharge；Ensure that electrolyte has the relatively low freezing point of ratio,
And give the resistance to combustion ability that electrolyte is the strongest simultaneously；Make the conductivity of ion within the scope of wider temperature good, keep positive pole and
On negative pole, electrochemical oxidation, reduction are stablized and are carried out, it is achieved taking into account of high/low temperature.
As preferably, the quality of described 5th additive and the quality of described non-aqueous organic solvent are 0.1-than span
0.4%。
Detailed description of the invention
Electrolyte prescription one: the non-aqueous organic solvent in electrolyte consists of 70% Allyl carbonate and (writes a Chinese character in simplified form PC, for volume
Ratio, lower same)+25% triethyl phosphate (TEP)；First additive is 2% vitamin C (VC)+3% ethylene carbonate (EC), lithium salts
For LiBF4And Li3PO4, lithium salts LiBF4Concentration is 0.1mol/L, Li3PO4Concentration be 0.01mol/L.
Electrolyte prescription two: non-aqueous organic solvent is Allyl carbonate and triethyl phosphate；Allyl carbonate and triethyl phosphate
Volume ratio be 80:20；
First additive is vitamin C and the compound additive of ethylene carbonate composition；Vitamin C and the volume of ethylene carbonate
Ratio is 4:2；
Electrolyte lithium salt LiBF4Concentration is 0.25mol/L, Li3PO4Concentration be 0.008mol/L.
Electrolyte prescription three: non-aqueous organic solvent is Allyl carbonate and triethyl phosphate；Allyl carbonate and triethyl phosphate
Volume ratio be 65:35；
First additive is vitamin C and the compound additive of ethylene carbonate composition；Vitamin C and the volume of ethylene carbonate
Ratio is 1:5；
Electrolyte lithium salt LiBF4Concentration is 0.05mol/L, Li3PO4Concentration be 0.02mol/L.
Electrolyte prescription four: with electrolyte prescription one, except for the difference that also includes Second addition in electrolyte, Second addition is
The additive that structural formula 1 represents:
[structural formula 1]
Wherein, R is CH3、C2H3、C6H6Alkyl and derivant thereof or C5H5N nitrogen heterocyclic ring aryl and derivant thereof.
The quality of Second addition and the quality of non-aqueous organic solvent are 0.1-0.4% than scope.
Electrolyte prescription five: with electrolyte prescription four, except for the difference that also includes the 3rd additive in electrolyte, the 3rd additive is
One or both in oxolane and 2-methyltetrahydrofuran.
The quality of the 3rd additive and the quality of non-aqueous organic solvent are 0.1-0.4% than span.
Electrolyte prescription six: with electrolyte prescription five, except for the difference that also includes the 4th additive in electrolyte, the 4th additive is
Vinylene carbonate, acrylonitrile, dimethyl sulfite, 1,3-propane sultone, fluorinated ethylene carbonate and trimethoxy
One or more in boroxane.
The quality of the 4th additive and the quality of described non-aqueous organic solvent are 0.1-0.4% than span.
Electrolyte prescription seven: with electrolyte prescription six, except for the difference that also includes the 5th additive in electrolyte, the 5th additive is
The additive that structural formula 2 represents:
[structural formula 2].
The quality of the 5th additive and the quality of described non-aqueous organic solvent are 0.1-0.4% than span.
Embodiment 1:
Use GHMG-M material with carbon element to be prepared as Carbon anode, use the electrolyte prescription one of the present invention as simulated battery electrolyte,
Using lithium metal as to electrode, 2032 button cells are utilized to investigate Carbon anode capacity in this electrolyte, under 25 degree of environment,
It is 351mAh/g that experiment records the capacity when 0.05C charge-discharge magnification；When 0.1C charge-discharge magnification, capacity is 348mAh/g；?
During 0.2C charge-discharge magnification, capacity is 337mAh/g.
Comparative example 1:
Use GHMG-M material with carbon element to be prepared as Carbon anode, use lithium-ion battery electrolytes conventional on market (to consist of 1M
LiPF6/EC+EMC+DMC, volume ratio is 1:1:1), as simulated battery electrolyte, using lithium metal as to electrode, utilize
Carbon anode capacity in this electrolyte investigated by 2032 button cells, and under 25 degree of environment, experiment records in 0.05C discharge and recharge times
During rate, capacity is 347mAh/g；When 0.1C charge-discharge magnification, capacity is 343mAh/g；When 0.2C charge-discharge magnification, capacity is
320mAh/g。
Embodiment 2:
Use GHMG-M material with carbon element to be prepared as Carbon anode, use the electrolyte prescription one of the present invention as simulated battery electrolyte,
Using lithium metal as to electrode, 2032 button cells are utilized to investigate Carbon anode capacity in this electrolyte, under 5 degree of environment,
It is 232mAh/g that experiment records the capacity when 0.05C charge-discharge magnification；When 0.1C charge-discharge magnification, capacity is 229mAh/g；?
During 0.2C charge-discharge magnification, capacity is 201mAh/g.
Comparative example 2:
Use GHMG-M material with carbon element to be prepared as Carbon anode, use lithium-ion battery electrolytes conventional on market (to consist of 1M
LiPF6/ EC+EMC+DMC, volume ratio is 1:1:1), as simulated battery electrolyte, using lithium metal as to electrode, utilize
Carbon anode capacity in this electrolyte investigated by 2032 button cells, and under 5 degree of environment, experiment records in 0.05C discharge and recharge times
During rate, capacity is 248mAh/g；When 0.1C charge-discharge magnification, capacity is 239mAh/g；When 0.2C charge-discharge magnification, capacity is
229mAh/g。
Embodiment 3:
Use GHMG-M material with carbon element to be prepared as Carbon anode, use the electrolyte prescription one of the present invention as simulated battery electrolyte,
Using lithium metal as to electrode, utilize 2032 button cells to investigate Carbon anode capacity in this electrolyte, spend environment-20
Under, it is 120mAh/g that experiment records the capacity when 0.05C charge-discharge magnification；When 0.1C charge-discharge magnification, capacity is 113mAh/
g；When 0.2C charge-discharge magnification, capacity is 93mAh/g.
Comparative example 3:
Use GHMG-M material with carbon element to be prepared as Carbon anode, use lithium-ion battery electrolytes conventional on market (to consist of 1M
LiPF6/ EC+EMC+DMC, volume ratio is 1:1:1), as simulated battery electrolyte, using lithium metal as to electrode, utilize
Carbon anode capacity in this electrolyte investigated by 2032 button cells, and under-20 degree environment, experiment records in 0.05C discharge and recharge
During multiplying power, capacity is 48mAh/g；When 0.1C charge-discharge magnification, capacity is 39mAh/g；When 0.2C charge-discharge magnification, capacity is
30mAh/g。
Embodiment 4:
Use GHMG-M material with carbon element to be prepared as Carbon anode, use the electrolyte prescription one of the present invention as simulated battery electrolyte,
Using lithium metal as to electrode, utilize 2032 button cells to investigate Carbon anode capacity in this electrolyte, spend environment-40
Under, it is 37mAh/g that experiment records the capacity when 0.05C charge-discharge magnification；When 0.1C charge-discharge magnification, capacity is 30mAh/g；
When 0.2C charge-discharge magnification, capacity is 21mAh/g.
Comparative example 4:
Use GHMG-M material with carbon element to be prepared as Carbon anode, use lithium-ion battery electrolytes conventional on market (to consist of 1M
LiPF6/ EC+EMC+DMC, volume ratio is 1:1:1), as simulated battery electrolyte, using lithium metal as to electrode, utilize
Carbon anode capacity in this electrolyte investigated by 2032 button cells, and under-40 degree environment, experiment records in 0.05C discharge and recharge
During multiplying power, capacity is 0mAh/g；When 0.1C charge-discharge magnification, capacity is 0mAh/g；When 0.2C charge-discharge magnification, capacity is
0mAh/g。
Embodiment 5:
Take electrolyte prescription of the present invention one 1 milliliters, uniformly drop on the steel disc of 0.5cm*10cm area, light one in atmosphere
End, flame quickly automatic distinguishing, there is remaining electrolyte not burn.
Comparative example 5:
On market, district, classical electrolyte 1 milliliter, uniformly drops on the steel disc of 0.5cm*10cm area, lights one end in atmosphere,
Flame from one end sustained combustion to the other end, will not automatic distinguishing, electrolyte all burns, and flame lightness is significantly greater than real
Execute the flame in example 5.
Embodiment 6-11
With embodiment one, except for the difference that using electrolyte prescription two-electrolyte prescription seven, under 25 degree of environment, experiment records
0.05C charge-discharge magnification, 0.1C charge-discharge magnification, at 0.2C charge-discharge magnification time capacity compared to the detection of embodiment one
Data rise successively.
Embodiment 12-17
With embodiment two, except for the difference that using electrolyte prescription two-electrolyte prescription seven, under 25 degree of environment, experiment records
0.05C charge-discharge magnification, 0.1C charge-discharge magnification, at 0.2C charge-discharge magnification time capacity compared to the detection of embodiment two
Data rise successively.
Above-described embodiment and corresponding comparative example illustrate, the electrolyte that the present invention provides has carbon under cryogenic property and bears
Pole function admirable, fire-retardant two big advantages.
This specific embodiment is only explanation of the invention, and it is not limitation of the present invention, people in the art
The present embodiment can be made after reading this specification by member as required does not has the amendment of creative contribution, but as long as at this
All protected by Patent Law in the right of invention.
Claims (10)
1. one kind can be filled miniature lithium battery electrolyte, it is characterised in that: it includes electrolyte lithium salt, non-aqueous organic solvent and first
Additive；
Described non-aqueous organic solvent is Allyl carbonate and triethyl phosphate；The volume ratio of Allyl carbonate and triethyl phosphate is
65-80:20-35；
Described first additive is vitamin C and the compound additive of ethylene carbonate composition；Vitamin C and ethylene carbonate
Volume ratio is 1-4:2-5；
Described electrolyte lithium salt is LiBF4And Li3PO4, LiBF4And Li3PO4Mass ratio be 8-12:1.
One the most according to claim 1 can fill miniature lithium battery electrolyte, it is characterised in that: described electrolyte lithium salt
LiBF4Concentration is 0.05-0.25mol/L, Li3PO4Concentration be 0.008-0.02mol/L.
One the most according to claim 2 can fill miniature lithium battery electrolyte, it is characterised in that: described electrolyte lithium salt
LiBF4Concentration is 0.1mol/L, Li3PO4Concentration be 0.01mol/L.
One the most according to claim 1 can fill miniature lithium battery electrolyte, it is characterised in that: described Allyl carbonate,
The volume ratio of triethyl phosphate, vitamin C and ethylene carbonate is 65-80:20-35:1-4:2-5.
One the most according to claim 4 can fill miniature lithium battery electrolyte, it is characterised in that: described Allyl carbonate,
The volume ratio of triethyl phosphate, vitamin C and ethylene carbonate is 70:25:2:3.
One the most according to claim 1 can fill miniature lithium battery electrolyte, it is characterised in that: described Allyl carbonate,
The volume ratio of triethyl phosphate is 68-75:20-30.
One the most according to claim 1 can fill miniature lithium battery electrolyte, it is characterised in that: described vitamin C and carbon
The volume ratio of vinyl acetate is 1-3:2-4.
8. can fill miniature lithium battery electrolyte according to the one described in any one of claim 1-7, it is characterised in that: electrolyte
In also include Second addition, described Second addition be structural formula 1 represent additive:
[structural formula 1]
Wherein, R is CH3、C2H3、C6H6Alkyl and derivant thereof or C5H5N nitrogen heterocyclic ring aryl and derivant thereof.
One the most according to claim 8 can fill miniature lithium battery electrolyte, it is characterised in that: electrolyte also includes
Three additives, described 3rd additive is one or both in oxolane and 2-methyltetrahydrofuran.
One the most according to claim 9 can fill miniature lithium battery electrolyte, it is characterised in that: electrolyte also includes
4th additive, described 4th additive be vinylene carbonate, acrylonitrile, dimethyl sulfite, 1, in 3-propane sulfonic acid
One or more in ester, fluorinated ethylene carbonate and trimethoxy boroxane.
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| CN106025338B (en) | 2018-11-06 |
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