CN108615941A - A kind of additive of anti-thermal runaway and its application in secondary lithium metal - Google Patents
A kind of additive of anti-thermal runaway and its application in secondary lithium metal Download PDFInfo
- Publication number
- CN108615941A CN108615941A CN201810388743.9A CN201810388743A CN108615941A CN 108615941 A CN108615941 A CN 108615941A CN 201810388743 A CN201810388743 A CN 201810388743A CN 108615941 A CN108615941 A CN 108615941A
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- China
- Prior art keywords
- lithium
- additive
- lithium metal
- battery
- ode
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- 239000000654 additive Substances 0.000 title claims abstract description 52
- 230000000996 additive effect Effects 0.000 title claims abstract description 52
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- -1 polypropylene Polymers 0.000 claims description 13
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000010416 ion conductor Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000001989 lithium alloy Substances 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
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- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 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
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- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001558 CF3SO3Li Inorganic materials 0.000 claims description 2
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
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- 229910003405 Li10GeP2S12 Inorganic materials 0.000 claims description 2
- 229910005317 Li14Zn(GeO4)4 Inorganic materials 0.000 claims description 2
- 229910010685 Li5La3M2O12 Inorganic materials 0.000 claims description 2
- 229910010850 Li6PS5X Inorganic materials 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- 229910012305 LiPON Inorganic materials 0.000 claims description 2
- 229910013461 LiZr2(PO4)3 Inorganic materials 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- MWQJGSUQGMJVCS-UHFFFAOYSA-N N=[S+]C(F)(F)F.[Li] Chemical compound N=[S+]C(F)(F)F.[Li] MWQJGSUQGMJVCS-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
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- 239000005864 Sulphur Substances 0.000 claims description 2
- 229910010252 TiO3 Inorganic materials 0.000 claims description 2
- QRVIVVYHHBRVQU-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O Chemical compound [Li+].[V+5].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O QRVIVVYHHBRVQU-UHFFFAOYSA-H 0.000 claims description 2
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- 229940072056 alginate Drugs 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- UFLFSNVZQRNKOX-UHFFFAOYSA-N carbonic acid;ethenyl acetate Chemical compound OC(O)=O.CC(=O)OC=C UFLFSNVZQRNKOX-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
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
- FGSXRUYPQWMIRU-UHFFFAOYSA-L lithium fluoro-dioxido-oxo-lambda5-phosphane iron(2+) Chemical compound P(=O)([O-])([O-])F.[Fe+2].[Li+] FGSXRUYPQWMIRU-UHFFFAOYSA-L 0.000 claims description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 2
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 claims description 2
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- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 210000003765 sex chromosome Anatomy 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
-
- 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
Abstract
The present invention relates to a kind of additive of anti-thermal runaway and its applications in secondary lithium metal.The end of the chain of the additive contains unsaturated double-bond and lithium an- ode interface film forming or flame retarding construction, stable SEI layers can be formed on lithium an- ode surface during circulating battery, contact of the lithium an- ode with electrolyte is not only increased, and makes its lithium metal battery assembled that there is excellent long circulating performance；On the other hand, the unsaturated double-bond of additive can absorb heat when battery overheats and polymerize, with containing fire-retardant group play the role of block burning, prevent battery thermal runaway.Present invention provides application of the above-mentioned additive in lithium metal battery.
Description
Technical field
The present invention relates to lithium metal battery field, the additive of specifically a kind of anti-thermal runaway and its secondary lithium gold
Belong to the application in battery.
Background technology
Lithium ion battery is due to energy density height, the advantages of good reliability, in mobile device, electric vehicle, intelligent grid
Equal fields achieve great development.However, commercialized lithium ion battery still has some potential safety problems, Yi Jineng at present
Metric density relatively low the problem of being difficult to meet the market demand.Using lithium metal as the lithium ion battery of cathode, there is highest theoretical ratio
Capacity（3860 mAhg-1）, minimum oxidation-reduction potential（- 3.04 V vs. standard hydrogen electrodes）, become energy storage field
" Holy grail "；Therefore, lithium metal battery is constructed as solving the problems, such as that current lithium ion battery energy density is difficult to meet the market demand
Important measure.However, lithium metal battery Presence of an interface is unstable, Li dendrite is easily grown, leads to shortening and the property of battery life
The decline of energy, and serious safety problem may be caused.This is because lithium is contacted with electrolyte can occur many side reactions, generate
The irreversible product of electrochemistry, to reduce the coulombic efficiency of lithium deposition and abjection process.In addition, lithium deposition and abjection process sheet
It is non-uniform in matter.During circulating battery, lithium metal can locally occur to deposit or deviate from speed, lead to this region
Larger volume expansion occurs.And this non-uniform volume expansion of lithium metal, it easily causes and becomes for breakable SEI layers in itself
Shape and rupture.Meanwhile the regions SEI of these ruptures have lower impedance in lithium deposition and stripping process, then further
The problem of exacerbating the side reaction of lithium an- ode interface and volume expansion exacerbates growth of the Li dendrite in rupture zone, serious to drop
The low cyclical stability of battery.If Li dendrite pierces through diaphragm, it will lead to battery short circuit, induction is caught fire or even the peaces such as explosion
Full problem.On the whole, this kind of insufficient key reason of high energy density cells performance is that SEI layers can not adapt to the dynamic of cathode
State volume change, rupture, which easily occurs, leads to the generation of more side reactions, and non-uniform lithium deposits and the growth of Li dendrite, to
The cycle performance for greatly reducing battery hinders its practical application.
In order to solve this problem, some significant trials have been carried out to optimize and stablize SEI layers in scientists,
Also it makes some progress.Currently, a kind of effective method is that film for additive is added in the electrolytic solution, to be passivated lithium metal
Negative terminal surface, stable, solid electrolyte interface layer is to prevent the further decomposition of electrolyte.For example, Archer seminars find
The liquid electrolyte for adding halide salt, has shown excellent room temperature long circulating stability, even if circulating beyond 1,000 times, SEI
Layer still maintains stable.Confirm that this SEI layers contains abundant fluoride salt through research（Mainly LiF）.This fluoride salt composition
SEI layers there is lower lithium ion diffusion impedance, reduce lithium ion and pass through SEI layers of activation energy, therefore improve battery
Cyclical stability（Nat. Mater., 2014, 13, 961）；Aurbach seminars in 2017 report addition carbonic acid fluorine
Electrolyte (the 1 M LiPF of vinyl acetate (FEC)6In EC/DMC) assembly Li/Li half-cells in 2 mA cm−2Electric current
Lower cycle has up to 3.3 mAh cm−2Face amount, the Li/ that can be circulated beyond 1100 circles, and assemble
LiNi0.6Co0.2Mn0.2O2 (NMC) full battery presents excellent cyclical stability（ACS Energy Lett. 2017, 2,
1321-1326）；Another method is to inhibit the life of Li dendrite using solid electrolyte or in lithium an- ode face coat
It is long, improve interface stability.In view of vinylene carbonate polymerized thylene carbonate second is formed in graphite cathode surface aggregate as additive
Enester can improve the stability at interface and the cycle performance of battery, this seminar is by vinylene carbonate in two isobutyl of azo
Nitrile causes lower in-situ polymerization and prepares solid polymer electrolyte, the LiCoO of assembling2/ Li batteries present the forthright again of dignity
Energy and fabulous cycle performance（Adv. Sci. 2017, 4, 1600377）；Cui Yi seminars apply on lithium an- ode surface
One layer has been covered by Cu3The artificial SEI films that N is constituted with polymeric binder.During circulating battery, artificial SEI layers can be in lithium
The SEI layers of piece Surface Creation high-lithium ion electric conductivity, high mechanical properties and excellent stability, to inhibit the growth of Li dendrite,
The SEI layers of integrality in cell operation is kept, to significantly improve the long circulating stability of battery（Adv.
Mater. 2017, 1605531）.Although by introducing additive or coating the side such as artificial SEI layers on lithium an- ode surface
Method can effectively inhibit lithium dendrite growth and improve the cycle performance of battery, but the interface problem of lithium an- ode does not still have
Obtain effective solution.In addition, in view of the potential safety problem of lithium metal battery, thermal runaway can be prevented by providing one kind, fire-retardant
Explosion-proof solution also has important value to the commercial applications of lithium metal battery.
To sum up, it constructs lithium metal battery and is difficult to meet asking for the market demand as current lithium ion battery energy density is solved
The important measure of topic.And the key for constructing this kind of high energy density cells is to optimize and stable, solid electrolyte interface.Although
Scientists make some progress in this field, but are not still solved the problem of lithium an- ode interface.
Therefore, heat to solve lithium an- ode interface stability sex chromosome mosaicism and is prevented by the method for introducing additive or solid electrolyte
It is out of control to improve the safety of battery, have great importance to the commercial applications of this high energy density cells.
Invention content
The purpose of the present invention is to provide a kind of additive of anti-thermal runaway and its applications in secondary lithium metal.
The technical solution adopted by the present invention is to achieve the above object：
Unsaturated double-bond is contained in additive end of the chain one end of a kind of additive of anti-thermal runaway, anti-thermal runaway, and the other end contains carbon
One kind in sour vinylene, fluorinated ethylene carbonate, sulfite, fluoro sulfite, phosphate, silane, sulfone structure.
The structure of the additive of the anti-thermal runaway is as shown in general formula 1：It is logical
Formula 1,
Wherein, the value of m, n are 0-2000, but are 0 when the value difference of m and n；A is CH2, carbonyl or unsubstituted；R1,
R1', R2, R2', R3Independently it is derived from H, halogen, methyl, CF3, CCl3, trimethyl silicon substrate, trimethyl silicane methyl or trimethyl silicane
Oxygroup；R is derived fromIn
One kind, wherein X, Y separately be selected from 6 alkyl below of carbon.
A kind of application of the additive of anti-thermal runaway in secondary lithium metal preparation.
A kind of secondary lithium metal, including lithium an- ode, anode, the diaphragm being placed between lithium an- ode and anode
And nonaqueous electrolyte, lithium an- ode surface apply additive described in claim 1 or nonaqueous electrolyte containing having the right to want
1 additive, wherein additive is asked to account for the 0.1% ~ 60% of nonaqueous electrolyte total weight.
The lithium an- ode is lithium metal or lithium alloy, and the form of lithium metal or lithium alloy is foil, piece, grain or powder；Institute
The active material for stating anode is cobalt acid lithium, LiFePO4, iron manganese phosphate for lithium, LiMn2O4, nickel ion doped, lithium-rich manganese-based, ternary material
Material, sulphur, sulfur compound, ferric sulfate lithium, lithium ion fluorophosphate, lithium vanadium fluorophosphate, lithium iron fluorophosphate, lithium manganese oxide
It is one or more of；The diaphragm material be cellulose non-woven film, alginate fibre nonwoven film, aramid fiber nonwoven film, aromatic polysulfonamide without
Spin one kind in film, polypropylene non-woven film, glass fibre, pet film, polyimides nonwoven film；Institute
The nonaqueous electrolyte stated includes lithium salts, organic substrate and inorganic lithium ion conductor.
The lithium salts is lithium hexafluoro phosphate（LiPF6）, lithium perchlorate (LiClO4), di-oxalate lithium borate (LiBOB), difluoro
Lithium bis (oxalate) borate (LiDFOB), trifluoromethanesulfonic acid lithium (CF3SO3Li), bis trifluoromethyl sulfimide lithium (LiTFSI), double fluorine sulphurs
One or several kinds in imide li (LiFSI)；Wherein lithium salts accounts for the 0% ~ 40% of lithium metal battery nonaqueous electrolyte total weight；
The organic substrate is ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, propene carbonate, diethyl carbonate, fourth two
Nitrile, adiponitrile, fluorinated ethylene carbonate, tetraethyleneglycol dimethyl ether, polymerized thylene carbonate vinyl acetate, polyacrylonitrile, polymethylacrylic acid
One or more of mixtures, organic substrate account for lithium metal in ester, polyethylene glycol oxide, poly- ethylene carbonate, polypropylene carbonate
The 0% ~ 70% of battery non-aqueous electrolyte total weight；The inorganic lithium ion conductor is Li3aLa(2/3)-aTiO3（0.04<a<
0.14）、Li3+aXaY1-aO4（X=Si、Sc、Ge、Ti；Y=P, As, V, Cr, 0<a<1）、LiZr2(PO4)3、Li7La3Zr2O12、Li1+ aAlaTi2-a(PO4)3（0<a<2）、Li1+aAlaGe2-a(PO4)3（0<a<2）、Li3OCl、Li3OCl0.5Br0.5、Li10GeP2S12、
Li14Zn(GeO4)4、Li5La3M2O12（M=Ta、Nb）、Li5.5La3Nb1.75In0.25O12、Li3N-LiX（X=Cl、Br、I）、Li9- naMaN2Cl3（M=Na, K, Rb, Cs, Mg, Al, 0<a<9,0<n<4）、3Li3N-MI（M=Li、Na、K）、LiPON、Li2S-MaSb（M=
Al, Si, P, 0<a<3,0<b<6）、Li6PS5X（X=F, Cl, Br, I）In one or several kinds, inorganic lithium ion conductor accounts for electrolysis
0 % ~ 99.9% of matter gross mass.
Lithium an- ode of the surface coated with additive is prepared via a method which：Additive is dissolved in solvent
In, solution is formed, then the solution containing additive is set 80 degree of vacuum drying chamber and dried and removed in lithium an- ode surface coating
Solvent obtains the lithium an- ode containing additive coating.
The solvent of the solubilising additive is dichloromethane, chloroform, Isosorbide-5-Nitrae-dioxane, glycol dimethyl ether, acetone, second
Nitrile, dimethyl sulfoxide (DMSO), sulfolane, dimethyl sulfite, sulfurous acid diethyl ester, tetrahydrofuran, 1,2- dichloroethanes, acetic acid second
Ester,NMethyl pyrrolidone,N,NDimethylformamide andN,NOne or more of dimethylacetylamide, additive account for molten
The 10% ~ 80% of liquid total weight.
The additive of thermal runaway and its application in secondary lithium metal are prevented the present invention relates to a kind of, is had following
Advantage：
1. additive itself contains more lithium ion conducting group, there is higher lithium ion conductivity, electrolysis will not be improved
Matter impedance；
2. additive can form stable SEI layers on lithium an- ode surface, lithium an- ode and electrolyte are not only increased
Contact, play the role of " binder ", and improve the conductivity of electrolyte, thus be conducive to improve battery cyclicity
Energy；
3. additive contains unsaturated double-bond, it can polymerize to form solid electrolyte with other comonomers, prepare high security
Solid state lithium battery；
4. due to battery can absorb heat rapidly when short circuit etc. causes overheat polymerisation occurs for the unsaturated double-bond of additive,
Close possible leakage region, flame-proof explosion-proof；The sulfoxide contained in polymer architecture or bound phosphate groups itself also have certain
Flame retardant property.
Technical solution of the present invention is easy to operate, has stronger innovative and important application value.The program can be applied
To the lithium metal battery of high-energy density, lithium alloy negative battery, solid state lithium battery（Including lithium-sulfur cell）And other are secondary
In high power lithium battery.
Description of the drawings
The long circulating performance for battery 1 C in room temperature that Fig. 1 embodiments 1 assemble.
The long circulating performance for battery 1 C in room temperature that Fig. 2 embodiments 2 assemble.
The long circulating performance for battery 0.2 C in room temperature that Fig. 3 embodiments 3 assemble.
The long circulating performance of 0.5 C under the battery room temperature that Fig. 4 embodiments 4 assemble.
The long circulating performance of 0.5 C under the battery room temperature that Fig. 5 embodiments 5 assemble.
The long circulating performance of 0.5 C under the battery room temperature that Fig. 6 embodiments 6 assemble.
Specific implementation mode
Embodiment 1
In glove box, by additive P1And P2's
Chloroformic solution（Mass ratio P1：P2=1:1,25 wt%）, it is coated on lithium foil, after standing and drying, obtains protecting containing additive
Layer（About 10 μm of thickness）Metallic lithium foil.Lithium foil containing matcoveredn is used in lithium ion battery, under 1 C charge and discharge, electricity
After 100 circle of pond cycle, specific discharge capacity still keeps 140 mAh/g or so, and stabilised efficiency is 99% or more.
Embodiment 2
In glove box, by additive P3The EC-DMC solution of 1M LiTFSI is added
In obtain electrolyte.For in lithium battery, under 0.5 C charge and discharge, after circulating battery 100 encloses, specific discharge capacity still to keep 125
mAh/g。
Embodiment 3
In glove box, by additive P4N,N-dimethylformamide solution（50
wt%）, it is coated in lithium piece, standing and drying.Additive protective layer will be contained（About 20 μm of thickness）Lithium piece be used for lithium-sulfur cell
In, under 0.2 C charge and discharge, after circulating battery 200 encloses, specific discharge capacity still keeps 890 mAh/g, efficiency to be maintained at 99.5%
More than.
Embodiment 4
In glove box, by additive P5（m=100, n = 80）With polyoxygenated
Ethylene（Mn = 800 kDa）And LiDFOB（Mass ratio=10:70:20）The mixed dissolution in dimethyl sulfoxide (DMSO), then with glass
Glass fiber is backing material, prepares electrolyte composite diaphragm, is applied in lithium metal powder/ternary material battery, from Fig. 4
In as can be seen that 0.5C under circulating battery 100 enclose after with 95% capacity retention ratio.
Embodiment 5
In glove box, by additive P6（m=200, n = 180）With
Li7La3Zr2O12In dimethyl sulfoxide (DMSO)（30 wt%）Solid electrolyte is made in middle mixed dissolution, tabletting, is assembled with positive and negative pole material
Battery.As shown in figure 5, after 100 circle cycles, the capacity retention ratio of battery can reach 93.5%.
Embodiment 6
In glove box, by additive P7（m=300, n = 30）Exist with lithium salts
N-Methyl pyrrolidone（20 wt%）After dissolving, the azodiisobutyronitrile of 0.5wt% is added, heating prepares polymer dielectric, and
Using cellulose non-woven film as backing material, electrolyte composite diaphragm is prepared.Assembled battery simultaneously tests respective battery performance,
As shown in fig. 6, battery has excellent cycle performance, still there is the capacity of 140mAh/g after 50 circles.
Test battery performance includes the following steps：
（1）The preparation of positive plate
A, by Kynoar（PVDF）It is dissolved inNIn methyl pyrrolidone, a concentration of 0.1 mol/L.
B, by PVDF, positive electrode active materials, conductive black with 10：80：After 10 mass ratio mixing, grind at least 1 hour.
C, the slurry obtained by upper step is equably scraped on aluminium foil, thickness is 100-120 mm, first 60oIt is done in C baking ovens
It is dry, then at 120oDry in C vacuum drying ovens, roll-in, punching continues after weighing 120oIt is dried in C vacuum drying ovens, is put in hand
It is spare in casing.
（2）The preparation of negative plate
A, PVDF is dissolved inNIn methyl pyrrolidone, a concentration of 0.1 mol/L.
B, by PVDF, negative electrode active material, conductive black with 10：80：After 10 mass ratio mixing, grind at least 1 hour.
C, the slurry obtained by upper step is equably scraped on copper foil, thickness is 100-120 mm, first 60oIt is done in C baking ovens
It is dry, then at 120oDry in C vacuum drying ovens, roll-in, punching continues after weighing 120oIt is dried in C vacuum drying ovens, is put in hand
It is spare in casing.
（3）Battery assembles
Corresponding half-cell or battery structure are placed in battery case, sealing obtains battery.
（4）Battery electrical property is tested
The long circulating performance and high rate performance of serondary lithium battery are tested with LAND battery charge and discharge instrument.
Claims (8)
1. a kind of additive of anti-thermal runaway, it is characterised in that：Unsaturated double-bond is contained in additive end of the chain one end of anti-thermal runaway,
The other end contains vinylene carbonate, fluorinated ethylene carbonate, sulfite, fluoro sulfite, phosphate, silane, sulfone knot
One kind in structure.
2. a kind of additive of anti-thermal runaway as described in claim 1, it is characterised in that：The structure of the additive such as general formula
Shown in 1：General formula 1,
Wherein, the value of m, n are 0-2000, but are 0 when the value difference of m and n；A is CH2, carbonyl or unsubstituted；R1,
R1', R2, R2', R3Independently it is derived from H, halogen, methyl, CF3, CCl3, trimethyl silicon substrate, trimethyl silicane methyl or trimethyl silicane
Oxygroup；R is derived from
In one kind, wherein X, Y separately be selected from 6 alkyl below of carbon.
3. a kind of application of the additive of anti-thermal runaway described in claim 1, it is characterised in that：A kind of addition of anti-thermal runaway
Application of the agent in secondary lithium metal preparation.
4. a kind of secondary lithium metal, including lithium an- ode, anode, the diaphragm that is placed between lithium an- ode and anode with
And nonaqueous electrolyte, it is characterised in that：Lithium an- ode surface applies additive or nonaqueous electrolyte described in claim 1 and contains
It has the right additive described in requirement 1, wherein additive accounts for the 0.1% ~ 60% of nonaqueous electrolyte total weight.
5. a kind of secondary lithium metal as described in claim 4, it is characterised in that：Lithium an- ode is that lithium metal or lithium close
The form of gold, lithium metal or lithium alloy is foil, piece, grain or powder；The active material of the anode is cobalt acid lithium, LiFePO4, phosphorus
Sour ferromanganese lithium, LiMn2O4, nickel ion doped, lithium-rich manganese-based, ternary material, sulphur, sulfur compound, ferric sulfate lithium, lithium ion fluorophosphoric acid
The one or more of salt, lithium vanadium fluorophosphate, lithium iron fluorophosphate, lithium manganese oxide；The diaphragm material is cellulose non-woven
Film, aramid fiber nonwoven film, aromatic polysulfonamide nonwoven film, polypropylene non-woven film, glass fibre, gathers to benzene two alginate fibre nonwoven film
One kind in formic acid glycol ester film, polyimides nonwoven film；The nonaqueous electrolyte includes lithium salts, organic substrate and nothing
Machine lithium ion conductor.
6. by a kind of secondary lithium metal described in claim 5, it is characterised in that：The lithium salts is lithium hexafluoro phosphate
（LiPF6）, lithium perchlorate (LiClO4), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiDFOB), trifluoromethanesulfonic acid
Lithium (CF3SO3Li), a kind of or several in bis trifluoromethyl sulfimide lithium (LiTFSI), double fluorine sulfimide lithiums (LiFSI)
Kind；Wherein lithium salts accounts for the 0% ~ 40% of lithium metal battery nonaqueous electrolyte total weight；The organic substrate is ethylene carbonate, carbon
Dimethyl phthalate, methyl ethyl carbonate, propene carbonate, diethyl carbonate, succinonitrile, adiponitrile, fluorinated ethylene carbonate, tetrem two
Diethylene glycol dimethyl ether, polymerized thylene carbonate vinyl acetate, polyacrylonitrile, polymethacrylates, polyethylene glycol oxide, poly- ethylene carbonate, poly- carbon
One or more of mixture in acid propylene ester, organic substrate account for the 0% ~ 70% of lithium metal battery nonaqueous electrolyte total weight；Institute
The inorganic lithium ion conductor stated is Li3aLa(2/3)-aTiO3（0.04<a<0.14）、Li3+aXaY1-aO4（X=Si、Sc、Ge、Ti；Y=P、
As, V, Cr, 0<a<1）、LiZr2(PO4)3、Li7La3Zr2O12、Li1+aAlaTi2-a(PO4)3（0<a<2）、Li1+aAlaGe2-a(PO4)3
（0<a<2）、Li3OCl、Li3OCl0.5Br0.5、Li10GeP2S12、Li14Zn(GeO4)4、Li5La3M2O12（M=Ta、Nb）、
Li5.5La3Nb1.75In0.25O12、Li3N-LiX（X=Cl、Br、I）、Li9-naMaN2Cl3（M=Na, K, Rb, Cs, Mg, Al, 0<a<9,0
<n<4）、3Li3N-MI（M=Li、Na、K）、LiPON、Li2S-MaSb（M=Al, Si, P, 0<a<3,0<b<6）、Li6PS5X（X=F,
Cl, Br, I）In one or several kinds, inorganic lithium ion conductor accounts for 0 % ~ 99.9% of electrolyte gross mass.
7. a kind of secondary lithium metal as described in claim 4, it is characterised in that：Surface is coated with the lithium metal of additive
Cathode is prepared via a method which：Additive is dissolved in solvent, solution is formed, the solution containing additive is negative in lithium metal
Pole surface film, then sets 80 degree of vacuum drying chamber and dries and removes solvent and obtain the lithium an- ode containing additive coating.
8. a kind of secondary lithium metal as described in claim 7, it is characterised in that：The solvent of solubilising additive is dichloromethane
Alkane, chloroform, Isosorbide-5-Nitrae-dioxane, glycol dimethyl ether, acetone, acetonitrile, dimethyl sulfoxide (DMSO), sulfolane, dimethyl sulfite, Asia
Dithyl sulfate, tetrahydrofuran, 1,2- dichloroethanes, ethyl acetate,NMethyl pyrrolidone,N,NDimethylformamide andN,NOne or more of dimethylacetylamide, additive account for the 10% ~ 80% of total solution weight.
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| CN109449486A (en) * | 2018-10-15 | 2019-03-08 | 苏州大学 | A kind of application of electrolysis additive |
| CN109818055A (en) * | 2019-02-24 | 2019-05-28 | 中国科学院青岛生物能源与过程研究所 | A kind of electrolyte of the anti-thermal runaway of width warm area and its serondary lithium battery of composition |
| CN110247111A (en) * | 2019-06-24 | 2019-09-17 | 中国科学院青岛生物能源与过程研究所 | A kind of solid polymer electrolyte containing sulfonic acid or phosphoric acid derivatives structure and its application in serondary lithium battery |
| CN110828897A (en) * | 2019-11-25 | 2020-02-21 | 中国科学院青岛生物能源与过程研究所 | Heat stress type thermal runaway prevention electrolyte and application thereof in secondary battery |
| CN112310481A (en) * | 2020-10-30 | 2021-02-02 | 山东海科新源材料科技股份有限公司 | Novel sulfur-containing additive and use thereof |
| CN114583172A (en) * | 2022-03-07 | 2022-06-03 | 中南大学 | Artificial SEI material, SEI film, preparation method of SEI film and application of SEI film in metal lithium battery |
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| CN109449486A (en) * | 2018-10-15 | 2019-03-08 | 苏州大学 | A kind of application of electrolysis additive |
| CN109818055A (en) * | 2019-02-24 | 2019-05-28 | 中国科学院青岛生物能源与过程研究所 | A kind of electrolyte of the anti-thermal runaway of width warm area and its serondary lithium battery of composition |
| CN110247111A (en) * | 2019-06-24 | 2019-09-17 | 中国科学院青岛生物能源与过程研究所 | A kind of solid polymer electrolyte containing sulfonic acid or phosphoric acid derivatives structure and its application in serondary lithium battery |
| CN110247111B (en) * | 2019-06-24 | 2022-03-29 | 中国科学院青岛生物能源与过程研究所 | Solid polymer electrolyte containing sulfonic acid or phosphoric acid derivative structure and application thereof in secondary lithium battery |
| CN110828897A (en) * | 2019-11-25 | 2020-02-21 | 中国科学院青岛生物能源与过程研究所 | Heat stress type thermal runaway prevention electrolyte and application thereof in secondary battery |
| CN112310481A (en) * | 2020-10-30 | 2021-02-02 | 山东海科新源材料科技股份有限公司 | Novel sulfur-containing additive and use thereof |
| CN112310481B (en) * | 2020-10-30 | 2021-12-14 | 山东海科新源材料科技股份有限公司 | Sulfur-containing additive and use thereof |
| CN114583172A (en) * | 2022-03-07 | 2022-06-03 | 中南大学 | Artificial SEI material, SEI film, preparation method of SEI film and application of SEI film in metal lithium battery |
| CN114583172B (en) * | 2022-03-07 | 2023-12-15 | 中南大学 | Artificial SEI material, SEI film, preparation thereof and application thereof in metal lithium battery |
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