CN103413969A - Electrolyte for lithium ion battery using silica-based material as negative electrode material and lithium ion battery - Google Patents
Electrolyte for lithium ion battery using silica-based material as negative electrode material and lithium ion battery Download PDFInfo
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- CN103413969A CN103413969A CN2013103231361A CN201310323136A CN103413969A CN 103413969 A CN103413969 A CN 103413969A CN 2013103231361 A CN2013103231361 A CN 2013103231361A CN 201310323136 A CN201310323136 A CN 201310323136A CN 103413969 A CN103413969 A CN 103413969A
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- lithium ion
- ion battery
- silica
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 118
- 239000000463 material Substances 0.000 title claims abstract description 74
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 68
- 239000007773 negative electrode material Substances 0.000 title abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract 6
- 239000000377 silicon dioxide Substances 0.000 title abstract 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000654 additive Substances 0.000 claims abstract description 40
- 230000000996 additive effect Effects 0.000 claims abstract description 40
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 26
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 25
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 25
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 29
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 24
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 23
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 21
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 15
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 14
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 8
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000085 borane Inorganic materials 0.000 claims description 6
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002210 silicon-based material Substances 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- -1 ethyl-methyl Chemical group 0.000 claims description 4
- 229910015044 LiB Inorganic materials 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 claims description 2
- 229930188620 butyrolactone Natural products 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229960000380 propiolactone Drugs 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 26
- 238000007599 discharging Methods 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- 238000006253 efflorescence Methods 0.000 abstract description 2
- 206010037844 rash Diseases 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 9
- 238000011056 performance test Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007787 solid Substances 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 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910018594 Si-Cu Inorganic materials 0.000 description 1
- 229910008465 Si—Cu Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 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 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 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
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910021484 silicon-nickel alloy Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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- 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 invention discloses an electrolyte for a lithium ion battery using a silica-based material as a negative electrode material and the lithium ion battery. The electrolyte comprises a lithium salt, a non-aqueous organic solvent and a film formation additive, wherein the non-aqueous organic solvent comprises ethylene carbonate; the film formation additive comprises TPFPB Tris(pentafluorophenyl) borane. The TPFPB in the electrolyte is used as the film formation additive of an SEI film, can facilitate the formation of the stable and integral SEI film on the surface of the negative electrode material, and can weaken an efflorescence phenomenon caused by a silicon volume effect when the silica-based material is used as the negative electrode material; the TPFPB can release freely moving lithium ions through the SEI film, so that part of lithium ions consumed during the formation process of the SEI film can be offset, lithium ion consumption can be lowered, and the charging and discharging efficiency and the cycle performance can be improved. The structural characteristic of the TPFPB determines that the TPFPB is relatively stable and not easy to decompose, so that the service life of the electrolyte is prolonged.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of electrolyte for lithium ion battery and the lithium ion battery of silica-base material as negative material of take.
Background technology
Lithium ion battery has the concern that the advantages such as energy density is high, good cycle are subject to people due to it, recent two decades has obtained development at full speed.Electric automobile mainly provides energy by lithium ion battery, and along with the progressively development of electric automobile, people have higher requirement to the energy density of lithium ion battery.Commercial lithium ion battery negative material adopts graphite cathode material at present, its charging and discharging capacity is lower, theoretical capacity is 372mAh/g, can not adapt to the miniaturization of current various portable electric appts and the electric automobile widespread demand to the large-capacity high-power chemical power source.
Silica-base material has become one of optimal candidate material that substitutes the graphite negative electrodes material, because it not only has high theoretical specific capacity (4200mAh/g), content is also very abundant simultaneously, yet, enclosed pasture efficiency first and poor cycle performance that silica-base material is low have limited its practical application, the main cause that hinders the application of silica-base material is that the silicon in silica-base material exists the enormousness effect in charge and discharge process, finally cause the silica-base material structure subside and silica-base material and electrolyte between the destruction of solid liquid interface layer.Lithium battery first circulation time due to electrolyte and negative material, react on aspect between solid liquid phase, so can form one deck SEI film.The SEI membrane interaction is as follows: the first, SEI film anticathode material can produce protective effect, makes material structure be not easy avalanche, increases the cycle life of electrode material.The second, SEI film can consume a part of lithium ion in production process, and the negative reaction process is exactly a process that lithium ion embeds and deviates from the interlayer structure of carbon in fact.So the formation of SEI film is to reduce negative pole cycle efficieny first.But, existing LiB (C
2O
4)
2(di-oxalate lithium borate) system electrolyte, LiPF
6(lithium hexafluoro phosphate) system electrolyte, due to its poorly conductive or can not form on silica-base material surface fine and close SEI film, thereby to have caused take silica-base material be low efficiency for charge-discharge and the poor cycle performance of the lithium ion battery of negative material, existingly take silica-base material and be difficult to adapt to practical application as the electrolyte of the lithium ion battery of negative material.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, a kind of electrolyte for lithium ion battery and the lithium ion battery of silica-base material as negative material of take is provided, this electrolyte helps to form and stablize complete SEI film on the negative material surface, and can discharge the lithium ion moved freely by the SEI film.
Solving technical scheme that the technology of the present invention problem adopts is to provide and a kind ofly take silica-base material and comprise as the electrolyte for lithium ion battery of negative material: lithium salts, non-aqueous organic solvent, film for additive, wherein, described non-aqueous organic solvent comprises ethylene carbonate (EC), and described film for additive comprises three (pentafluorophenyl group) borine (TPFPB).
Preferably, the content of described three (pentafluorophenyl group) borine is 1%～7% of described electrolyte total weight.
Preferably, described film for additive also comprises vinylene carbonate (VC), vinylethylene carbonate (VEC), 1,3-sulfonic acid propiolactone (1,3-PS), Isosorbide-5-Nitrae-sulfonic acid butyrolactone (in Isosorbide-5-Nitrae-BS) one or more.
Preferably, the content of all the other film for additive except described three (pentafluorophenyl group) borine in film for additive is 2%～5% of described electrolyte total weight.
Preferably, described lithium salts is LiPF
6, LiClO
4, LiB (C
2O
4)
2In one or more.
Preferably, the concentration of described lithium salts is 0.5M～1.2M.
Preferably, described non-aqueous organic solvent also comprises one or more in diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl-methyl carbonic ester (EMC), fluorinated ethylene carbonate (FEC).
Preferably, described silica-base material is one or more in silicon materials, Si-C composite material, aluminosilicate alloy material.
The present invention also provides a kind of lithium ion battery, comprises above-mentioned electrolyte.
In the present invention, using the film for additive of the TPFPB of silica-base material in the electrolyte for lithium ion battery of negative material as the SEI film, help to form and stablize complete solid electrolyte membrane (SEI film) on the negative material surface, the powder phenomenon-tion that the bulk effect of the silicon while weakening silica-base material as negative material causes, and TPFPB can discharge the lithium ion moved freely by the SEI film, will balance out like this part lithium ion consumed in the forming process of SEI film, reduce lithium ion consumption, improve efficiency for charge-discharge and cycle performance.And the design feature of TPFPB has determined himself more stable being not easy decomposition, the life-span of having improved electrolyte.
The accompanying drawing explanation
The charge-discharge performance resolution chart of Fig. 1 lithium ion battery that to be the embodiment of the present invention 1 make respectively with the electrolyte in Comparative Examples 1.
Embodiment
For making those skilled in the art understand better technical scheme of the present invention, below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment 1
The present embodiment provides a kind of take Si-C composite material and is the electrolyte for lithium ion battery of negative material, comprising: lithium salts LiPF
6, wherein, the mass ratio of EC, DEC and FEC is EC:DEC:FEC=6:3:1 for non-aqueous organic solvent EC, DEC and FEC(), film for additive VC and TPFPB.Wherein, LiPF
6Concentration be 1M, the content of VC is 2% of described electrolyte total weight, the content of TPFPB is 5% of described electrolyte total weight.
The compound method of this electrolyte is as follows: by lithium salts LiPF
6Be dissolved in the mixed solvent of non-aqueous organic solvent EC, DEC and FEC, wherein, the mass ratio of EC, DEC and FEC is EC:DEC:FEC=6:3:1, LiPF
6Concentration be 1M; And then in this solution, add film for additive VC, then add film for additive TPFPB, obtain electrolyte.Wherein, the content of VC is 2% of described electrolyte total weight, and the content of TPFPB is 5% of described electrolyte total weight.
In lithium ion battery, the formation of SEI film can produce vital impact to electrode material especially negative material, and on the one hand, the formation of SEI film has consumed the part lithium ion, make the first charge-discharge irreversible capacity increase, reduced the efficiency for charge-discharge of negative material; On the other hand, it is insoluble that the SEI film has organic solvent, energy stable existence in organic electrolyte solution, and solvent molecule can not pass through this passivating film, thereby can effectively prevent the common embedding of solvent molecule, avoided because solvent molecule embeds the destruction that the anticathode material causes altogether, thereby greatly improved cycle performance and the useful life of negative pole.
Si-C composite material in the present embodiment be TPFPB in the electrolyte for lithium ion battery of negative material as the film for additive of SEI film, help to form and stablize complete SEI film on the negative material surface.TPFPB not only has the effect that promotes to form the SEI film on negative material, and TPFPB has more effect with respect to film for additive VC of the prior art etc. simultaneously.The electronegativity of the fluorine connected on the phenyl in TPFPB is very strong, five fluorine and phenyl have strong conjugation, make pentafluorophenyl group become very strong electron-withdrawing group, and pentafluorophenyl group is strong is attracting the electronics around boron, thereby make the cloud density around boron greatly reduce, boron just has very strong Lewis acidity like this, and boron itself is electron-defect compound, therefore, TPFPB be easy to the SEI film in inert substance such as LiF, Li
2O, Li
2O
2Deng reaction, the solubility of these several materials in electrolyte is increased, this process discharges the lithium ion moved freely, thereby has increased the conductivity of electrolyte, and the circulation of negative material and high rate performance all can improve accordingly like this.TPFPB is conducive to form more stable SEI film, improves the stability of negative material top layer molecular film, reduces the common embedding of solvent molecule.And the design feature of TPFPB has determined himself more stable being not easy decomposition, the life-span of having improved electrolyte.
In addition on the one hand, in the forming process of SEI film, consumed the part lithium ion, and because the TPFPB in electrolyte can discharge the lithium ion moved freely by the SEI film, will balance out like this part lithium ion consumed in the forming process of SEI film, thereby reduce the first charge-discharge irreversible capacity of negative material.
Silica-base material is poor as the cycle performance of negative material, for example, Si-C composite material in the present embodiment, exactly because the bulk effect of Si-C composite material causes its outer SEI film cracking efflorescence formed, in the charge and discharge cycles process, will ceaselessly regenerate the SEI film like this, thereby ceaselessly consume the lithium in the lithium salts in electrolyte.And the TPFPB in electrolyte can discharge the lithium ion moved freely by the SEI film, so just greatly reduced the loss of the lithium in the lithium salts in electrolyte.
In sum, TPFPB in electrolyte promotes to have formed more stable SEI film, lithium ion battery is in charge and discharge process, the powder phenomenon-tion of the bulk effect of the silicon in the negative electrode active material Si-C composite material on negative pole just weakens, make the efficiency for charge-discharge of battery improve, cycle performance is corresponding being improved also.
Si-C composite material in the present embodiment is to have added a small amount of VC in the electrolyte for lithium ion battery of negative material, the one, promote film forming, and the interpolation of the 2nd, VC is proved to be the cycle performance that can improve battery.Therefore, in the electrolyte in this enforcement, two kinds of film for additive actings in conjunction of preferred TPFPB and VC promote the formation of SEI films.
Si-C composite material in the present embodiment is that the EC in the electrolyte for lithium ion battery of negative material has resistant to elevated temperatures effect, due to battery, has relatively high temperature in charge and discharge process, so preferred EC is as the non-aqueous organic solvent in the electrolyte in the present embodiment.And DEC, DMC, EMC, FEC have good conductivity, in the present embodiment, preferred DEC, FEC and EC are jointly as non-aqueous organic solvent.
The present embodiment also provides a kind of lithium ion battery, comprises above-mentioned electrolyte.
The negative electrode active material used in the lithium ion battery process for preparation in the present embodiment is Si-C composite material, battery manufacturing process is as follows: negative active core-shell material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10, use the NMP(1-N-methyl-2-2-pyrrolidone N-) this mixture is modulated into to slurry, evenly be coated on Copper Foil, 100 ℃ of vacuumize 24 hours, make the experimental cell pole piece.Take the lithium sheet as to electrode, and electrolyte is the above-mentioned electrolyte prepared, and barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
As shown in Figure 1, the button cell that the electrolyte of the present embodiment preparation is made carries out the charge-discharge performance test: charging and discharging currents is 0.2CA, and the charging/discharging voltage interval is 0.01～1.5V, circulates after 50 times, and the battery capacity conservation rate is about 87%.
Comparative Examples 1
This Comparative Examples provides a kind of take Si-C composite material and is the electrolyte for lithium ion battery of negative material, comprising: lithium salts LiPF
6, wherein, the mass ratio of EC, DEC and FEC is EC:DEC:FEC=6:3:1 for non-aqueous organic solvent EC, DEC and FEC(), film for additive VC.Wherein, LiPF
6Concentration be 1M, the content of VC is 7% of described electrolyte total weight.
The compound method of this electrolyte is as follows: by lithium salts LiPF
6Be dissolved in the mixed solvent of non-aqueous organic solvent EC, DEC and FEC, wherein, the mass ratio of EC, DEC and FEC is EC:DEC:FEC=6:3:1, LiPF
6Concentration be 1M; And then in this solution, add film for additive VC, obtain electrolyte.Wherein, the content of VC is 7% of described electrolyte total weight.
As shown in Figure 1, method according to preparation button cell in embodiment 1, use the electrolyte of this Comparative Examples preparation to make button cell, and this battery is carried out to the charge-discharge performance test: charging and discharging currents is 0.2CA, the charging/discharging voltage interval is 0.01～1.5V, circulate after 50 times, the battery capacity conservation rate is about 71%.
The lithium ion battery that the lithium ion battery made of electrolyte of preparation in embodiment 1 is made with respect to the electrolyte of preparation in this Comparative Examples 1 is after charge and discharge cycles 50 times, and the capability retention of battery is higher, and the cycle performance of battery is better.
Embodiment 2
The present embodiment provides a kind of take silicon materials and is the electrolyte for lithium ion battery of negative material, comprising: lithium salts LiClO
4, wherein, the mass ratio of EC, DEC and DMC is EC:DEC:DMC=4:4:2 for non-aqueous organic solvent EC, DEC and DMC(), film for additive VC and TPFPB.Wherein, LiClO
4Concentration be 0.5M, the content of VC is 2% of described electrolyte total weight, the content of TPFPB is 2% of described electrolyte total weight.
The compound method of this electrolyte is as follows: by lithium salts LiClO
4Be dissolved in the mixed solvent of non-aqueous organic solvent EC, DEC and DMC, wherein, the mass ratio of EC, DEC and DMC is EC:DEC:DMC=4:4:2, LiClO
4Concentration be 0.5M; And then in this solution, add film for additive VC, then add film for additive TPFPB, obtain electrolyte.Wherein, the content of VC is 2% of described electrolyte total weight, and the content of TPFPB is 2% of described electrolyte total weight.
The present embodiment also provides a kind of lithium ion battery, comprises above-mentioned electrolyte.
Method according to preparation button cell in embodiment 1, use the electrolyte of the present embodiment preparation to make button cell, and this battery is carried out to the charge-discharge performance test: charging and discharging currents is 0.2CA, the charging/discharging voltage interval is 0.01～1.5V, circulate after 50 times, the battery capacity conservation rate is about 79.4%.
Embodiment 3
The present embodiment provides a kind of take Si-Cu alloy material and is the electrolyte for lithium ion battery of negative material, comprising: lithium salts LiPF
6And LiClO
4, wherein, the mass ratio of EC, EMC and DMC is EC:EMC:DMC=4:3:3 for non-aqueous organic solvent EC, EMC and DMC(), film for additive VC, VEC and TPFPB.Wherein, LiPF
6Concentration be 0.6M, LiClO
4Concentration be 0.4M, the content of VC is 2% of described electrolyte total weight, the content of VEC is 1% of described electrolyte total weight, the content of TPFPB is 4% of described electrolyte total weight.
The compound method of this electrolyte is as follows: by lithium salts LiPF
6And LiClO
4Be dissolved in the mixed solvent of non-aqueous organic solvent EC, EMC and DMC, wherein, the mass ratio of EC, EMC and DMC is EC:EMC:DMC=4:3:3, LiPF
6Concentration be 0.6M, LiClO
4Concentration be 0.4M; And then in this solution, add film for additive VC, then add film for additive VEC, then add film for additive TPFPB, obtain electrolyte.Wherein, the content of VC is 2% of described electrolyte total weight, and the content of VC is 1% of described electrolyte total weight, and the content of TPFPB is 4% of described electrolyte total weight.
The present embodiment also provides a kind of lithium ion battery, comprises above-mentioned electrolyte.
Method according to preparation button cell in embodiment 1, use the electrolyte of the present embodiment preparation to make button cell, and this battery is carried out to the charge-discharge performance test: charging and discharging currents is 0.2CA, the charging/discharging voltage interval is 0.01～1.5V, circulate after 50 times, the battery capacity conservation rate is about 80.7%.
Embodiment 4
The present embodiment provides a kind of take Si-C composite material and is the electrolyte for lithium ion battery of negative material, comprising: lithium salts LiB (C
2O
4)
2, wherein, the mass ratio of EC and DMC is EC:DMC=4:3 for non-aqueous organic solvent EC and DMC(), film for additive 1,3-PS and TPFPB.Wherein, LiB (C
2O
4)
2Concentration be 0.8M, the content of 1,3-PS is 4% of described electrolyte total weight, the content of TPFPB is 1% of described electrolyte total weight.
The compound method of this electrolyte is as follows: by lithium salts LiB (C
2O
4)
2Be dissolved in the mixed solvent of non-aqueous organic solvent EC and DMC, wherein, the mass ratio of EC and DMC is EC:DMC=4:3, LiB (C
2O
4)
2Concentration be 0.8M; And then in this solution, add film for additive 1,3-PS, then add film for additive TPFPB, obtain electrolyte.Wherein, the content of 1,3-PS is 4% of described electrolyte total weight, and the content of TPFPB is 1% of described electrolyte total weight.
The present embodiment also provides a kind of lithium ion battery, comprises above-mentioned electrolyte.
Method according to preparation button cell in embodiment 1, use the electrolyte of the present embodiment preparation to make button cell, and this battery is carried out to the charge-discharge performance test: charging and discharging currents is 0.2CA, the charging/discharging voltage interval is 0.01～1.5V, circulate after 50 times, the battery capacity conservation rate is about 85.3%.
Embodiment 5
The present embodiment provides a kind of take Si-C composite material and is the electrolyte for lithium ion battery of negative material, comprising: lithium salts LiB (C
2O
4)
2And LiClO
4, wherein, the mass ratio of EC, DEC and EMC is EC:DEC:EMC=2:2:4 for non-aqueous organic solvent EC, DEC and EMC(), film for additive TPFPB.Wherein, LiB (C
2O
4)
2Concentration be 0.5M, LiClO
4Concentration be 0.5M, the content of TPFPB is 7% of described electrolyte total weight.
The compound method of this electrolyte is as follows: by lithium salts LiB (C
2O
4)
2And LiClO
4Be dissolved in the mixed solvent of non-aqueous organic solvent EC, DEC and EMC, wherein, the mass ratio of EC, DEC and EMC is EC:DEC:EMC=2:2:4, LiB (C
2O
4)
2Concentration be 0.5M, LiClO
4Concentration be 0.5M; And then in this solution, add film for additive TPFPB, obtain electrolyte.Wherein, the content of TPFPB is 7% of described electrolyte total weight.
The present embodiment also provides a kind of lithium ion battery, comprises above-mentioned electrolyte.
Method according to preparation button cell in embodiment 1, use the electrolyte of the present embodiment preparation to make button cell, and this battery is carried out to the charge-discharge performance test: charging and discharging currents is 0.2CA, the charging/discharging voltage interval is 0.01～1.5V, circulate after 50 times, the battery capacity conservation rate is about 83.5%.
Embodiment 6
The present embodiment provides a kind of and take Si-C composite material and silicon materials as the electrolyte for lithium ion battery (wherein, the mass ratio of Si-C composite material and silicon materials is 1:1) of negative material, comprising: lithium salts LiB (C
2O
4)
2And LiPF
6, wherein, the mass ratio of EC, FEC and EMC is EC:FEC:EMC=3:3:4 for non-aqueous organic solvent EC, FEC and EMC(), film for additive Isosorbide-5-Nitrae-BS and TPFPB.Wherein, LiB (C
2O
4)
2Concentration be 0.7M, LiPF
6Concentration be 0.3M, the content of Isosorbide-5-Nitrae-BS is 3% of described electrolyte total weight, the content of TPFPB is 3% of described electrolyte total weight.
The compound method of this electrolyte is as follows: by lithium salts LiB (C
2O
4)
2And LiPF
6Be dissolved in the mixed solvent of non-aqueous organic solvent EC, FEC and EMC, wherein, the mass ratio of EC, FEC and EMC is EC:FEC:EMC=3:3:4, LiB (C
2O
4)
2Concentration be 0.7M, LiPF
6Concentration be 0.3M; And then in this solution, add film for additive Isosorbide-5-Nitrae-BS, then add film for additive TPFPB, obtain electrolyte.Wherein, the content of Isosorbide-5-Nitrae-BS is 3% of described electrolyte total weight, and the content of TPFPB is 3% of described electrolyte total weight.
The present embodiment also provides a kind of lithium ion battery, comprises above-mentioned electrolyte.
Method according to preparation button cell in embodiment 1, use the electrolyte of the present embodiment preparation to make button cell, and this battery is carried out to the charge-discharge performance test: charging and discharging currents is 0.2CA, the charging/discharging voltage interval is 0.01～1.5V, circulate after 50 times, the battery capacity conservation rate is about 79.6%.
Embodiment 7
The present embodiment provides a kind of take the silicon nickel alloy material and is the electrolyte for lithium ion battery of negative material, comprising: lithium salts LiPF
6, non-aqueous organic solvent EC, film for additive Isosorbide-5-Nitrae-BS and TPFPB.Wherein, LiPF
6Concentration be 1.2M, the content of Isosorbide-5-Nitrae-BS is 5% of described electrolyte total weight, the content of TPFPB is 4% of described electrolyte total weight.
The compound method of this electrolyte is as follows: by lithium salts LiPF
6Be dissolved in non-aqueous organic solvent EC, wherein, LiPF
6Concentration be 1.2M; And then in this solution, add film for additive Isosorbide-5-Nitrae-BS, then add film for additive TPFPB, obtain electrolyte.Wherein, the content of Isosorbide-5-Nitrae-BS is 5% of described electrolyte total weight, and the content of TPFPB is 4% of described electrolyte total weight.
The present embodiment also provides a kind of lithium ion battery, comprises above-mentioned electrolyte.
Method according to preparation button cell in embodiment 1, use the electrolyte of the present embodiment preparation to make button cell, and this battery is carried out to the charge-discharge performance test: charging and discharging currents is 0.2CA, the charging/discharging voltage interval is 0.01～1.5V, circulate after 50 times, the battery capacity conservation rate is about 82.5%.
Be understandable that, above execution mode is only the illustrative embodiments adopted for principle of the present invention is described, yet the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement also are considered as protection scope of the present invention.
Claims (9)
1. take the electrolyte for lithium ion battery of silica-base material as negative material for one kind, comprise: lithium salts, non-aqueous organic solvent, film for additive, wherein, described non-aqueous organic solvent comprises ethylene carbonate, it is characterized in that, described film for additive comprises three (pentafluorophenyl group) borine.
2. according to claim 1ly take silica-base material and be the electrolyte for lithium ion battery of negative material, it is characterized in that, the content of described three (pentafluorophenyl group) borine is 1%～7% of described electrolyte total weight.
3. according to claim 1ly take the electrolyte for lithium ion battery of silica-base material as negative material, it is characterized in that, described film for additive also comprises vinylene carbonate, vinylethylene carbonate, 1, in 3-sulfonic acid propiolactone, Isosorbide-5-Nitrae-sulfonic acid butyrolactone one or more.
4. according to claim 3ly take the electrolyte for lithium ion battery of silica-base material as negative material, it is characterized in that, the content of all the other film for additive except described three (pentafluorophenyl group) borine in film for additive is 2%～5% of described electrolyte total weight.
5. according to claim 1ly take silica-base material and be the electrolyte for lithium ion battery of negative material, it is characterized in that, described lithium salts is LiPF
6, LiClO
4, LiB (C
2O
4)
2In one or more.
6. according to claim 1ly take silica-base material and be the electrolyte for lithium ion battery of negative material, it is characterized in that, the concentration of described lithium salts is 0.5M～1.2M.
7. according to claim 1ly take the electrolyte for lithium ion battery of silica-base material as negative material, it is characterized in that, described non-aqueous organic solvent also comprises one or more in diethyl carbonate, dimethyl carbonate, ethyl-methyl carbonic ester, fluorinated ethylene carbonate.
8. according to claim 1ly take silica-base material and be the electrolyte for lithium ion battery of negative material, it is characterized in that, described silica-base material is one or more in silicon materials, Si-C composite material, aluminosilicate alloy material.
9. a lithium ion battery, is characterized in that, comprises the described electrolyte of claim 1～8 any one.
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| CN105470563A (en) * | 2015-01-28 | 2016-04-06 | 万向A一二三***有限公司 | Lithium ion battery electrolyte suitably used for silicon-carbon negative electrode |
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Cited By (4)
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| CN105470563A (en) * | 2015-01-28 | 2016-04-06 | 万向A一二三***有限公司 | Lithium ion battery electrolyte suitably used for silicon-carbon negative electrode |
| CN106410267A (en) * | 2016-11-11 | 2017-02-15 | 上海空间电源研究所 | Silicon-based lithium ion secondary battery with high specific energy and preparation method of lithium ion secondary battery |
| CN107055574A (en) * | 2017-04-10 | 2017-08-18 | 多氟多化工股份有限公司 | A kind of method of purification of lithium hexafluoro phosphate |
| CN108470939A (en) * | 2018-03-31 | 2018-08-31 | 广东天劲新能源科技股份有限公司 | A kind of heat safe electrolyte of big multiplying power and lithium ion battery |
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|---|---|
| CN103413969B (en) | 2016-12-28 |
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