CN103413969B - A kind of electrolyte for lithium ion battery with silica-base material as negative material and lithium ion battery - Google Patents
A kind of electrolyte for lithium ion battery with silica-base material as negative material and lithium ion battery Download PDFInfo
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- CN103413969B CN103413969B CN201310323136.1A CN201310323136A CN103413969B CN 103413969 B CN103413969 B CN 103413969B CN 201310323136 A CN201310323136 A CN 201310323136A CN 103413969 B CN103413969 B CN 103413969B
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- lithium ion
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- ion battery
- silica
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 103
- 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 60
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 60
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000654 additive Substances 0.000 claims abstract description 37
- 230000000996 additive effect Effects 0.000 claims abstract description 37
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 25
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 25
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 22
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims abstract description 8
- 229910000085 borane Inorganic materials 0.000 claims abstract description 7
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 7
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 24
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 23
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 15
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 5
- 239000002210 silicon-based material Substances 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 claims description 2
- 229960000380 propiolactone Drugs 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims 2
- AOANMOLKQQXRCC-UHFFFAOYSA-N C(C)(=O)OC=C.C(O)(=O)F Chemical compound C(C)(=O)OC=C.C(O)(=O)F AOANMOLKQQXRCC-UHFFFAOYSA-N 0.000 claims 1
- 229910000323 aluminium silicate Inorganic materials 0.000 claims 1
- 229930188620 butyrolactone Natural products 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 26
- 230000008569 process Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 239000010703 silicon Substances 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 238000010276 construction Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 28
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 20
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 13
- 238000007599 discharging Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 238000011056 performance test Methods 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 7
- -1 alkene ester Chemical class 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006378 damage Effects 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
- 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
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001323 Li2O2 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910000676 Si alloy Inorganic materials 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
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material 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
- 238000000280 densification Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 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
- 150000002596 lactones Chemical class 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000005486 organic electrolyte 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
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 206010037844 rash Diseases 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
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- 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 a kind of electrolyte for lithium ion battery with silica-base material as negative material and lithium ion battery, this electrolyte includes: lithium salts, non-aqueous organic solvent, film for additive, wherein, described non-aqueous organic solvent includes that ethylene carbonate, described film for additive include three (pentafluorophenyl group) borine.TPFPB in this electrolyte is as the film for additive of SEI film, contribute to being formed on negative material surface stablizing complete SEI film, weaken the powder phenomenon-tion that silica-base material causes as the bulk effect of silicon during negative material, and TPFPB can discharge the lithium ion moved freely by SEI film, thus can balance out the 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 construction features of TPFPB determines himself more stable being not easy and decomposes, improve the life-span of electrolyte.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of with silica-base material
Electrolyte for lithium ion battery and lithium ion battery for negative material.
Background technology
Lithium ion battery has the advantages such as energy density height, good cycle due to it and is subject to
To the concern of people, recent two decades has obtained development at full speed.Electric automobile mainly by
Lithium ion battery provides energy, and along with the progressively development of electric automobile, people are to lithium ion
The energy density of battery is had higher requirement.The most commercial lithium ion battery negative
Material uses graphite cathode material, and its charging and discharging capacity is relatively low, and theoretical capacity is
372mAh/g, does not the most adapt to the miniaturization of current various portable electric appts and electronic
The automobile widespread demand to large-capacity high-power electrochmical power source.
Silica-base material become substitute graphite negative electrodes material optimal candidate material it
One, because it does not only have high theoretical specific capacity (4200mAh/g), content yet pole simultaneously
Horn of plenty, but, coulombic efficiency first and the cycle performance of difference that silica-base material is low limit
Its actual application, the main cause hindering the application of silica-base material is in silica-base material
Silicon in charge and discharge process, there is enormousness effect, ultimately result in silica-base material knot
Subsiding and the destruction of solid liquid interface layer between silica-base material and electrolyte of structure.At lithium electricity
Occur anti-between solid liquid phase in aspect due to electrolyte and negative material when pond is circulated first
Should, so one layer of SEI film can be formed.SEI membrane interaction is as follows: first, SEI film is to negative
Pole material can produce protective effect, makes material structure be not easy avalanche, increases electrode material
Cycle life.Second, SEI film can consume a part of lithium ion during producing, and
Negative reaction process is exactly Lithium-ion embeding and an abjection in the interlayer structure of carbon in fact
A process.So the formation of SEI film can reduce negative pole cycle efficieny first.
But, existing LiB (C2O4)2(di-oxalate lithium borate) system electrolyte, LiPF6
(lithium hexafluoro phosphate) system electrolyte, due to its poorly conductive or can not be at silica-base material
Surface forms the SEI film of densification, has thus resulted in the lithium with silica-base material as negative material
The low efficiency for charge-discharge of ion battery and the cycle performance of difference, existing with silica-base material be
The electrolyte of the lithium ion battery of negative material is difficult in adapt to actual application.
Summary of the invention
The technical problem to be solved be for present in prior art above-mentioned not
Foot, it is provided that a kind of electrolyte for lithium ion battery with silica-base material as negative material and lithium
Ion battery, this electrolyte contributes to being formed on negative material surface stablizing complete SEI
Film, and the lithium ion moved freely can be discharged by SEI film.
Solve the technology of the present invention problem and be employed technical scheme comprise that offer is a kind of with silicon substrate
Material includes for the electrolyte for lithium ion battery of negative material: lithium salts, non-aqueous organic solvent,
Film for additive, wherein, described non-aqueous organic solvent includes ethylene carbonate (EC),
Described film for additive includes three (pentafluorophenyl group) borine (TPFPB).
Preferably, the content of described three (pentafluorophenyl group) borine is that described electrolyte is total
The 1%～7% of weight.
Preferably, described film for additive also includes vinylene carbonate (VC), carbon
Acid vinylethylene (VEC), 1,3-sulfonic acid propiolactone (1,3-PS), 1,4-sulfonic acid fourth
In lactone (1,4-BS) one or more.
Preferably, in film for additive in addition to described three (pentafluorophenyl group) borine
The content of remaining film for additive is the 2%～5% of described electrolyte gross weight.
Preferably, described lithium salts is LiPF6、LiClO4、LiB(C2O4)2In one
Or it is several.
Preferably, the concentration of described lithium salts is 0.5M～1.2M.
Preferably, described non-aqueous organic solvent also include diethyl carbonate (DEC),
Dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), fluoro ethylene
In alkene ester (FEC) one or more.
Preferably, described silica-base material is silicon materials, Si-C composite material, silicon alloy
One or more in material.
The present invention also provides for a kind of lithium ion battery, including above-mentioned electrolyte.
In the electrolyte for lithium ion battery with silica-base material as negative material in the present invention
TPFPB as the film for additive of SEI film, contribute to being formed on negative material surface
Stablize complete solid electrolyte membrane (SEI film), weaken silica-base material as negative material
Time the powder phenomenon-tion that causes of the bulk effect of silicon, and TPFPB can be discharged by SEI film
The lithium ion out moved freely, thus can balance out in the forming process of SEI film and disappear
The part lithium ion of consumption, reduces lithium ion consumption, improves efficiency for charge-discharge and cycle performance.
And the construction features of TPFPB determines himself more stable being not easy and decomposes, improve
The life-span of electrolyte.
Accompanying drawing explanation
Fig. 1 is the lithium that the embodiment of the present invention 1 is respectively prepared with the electrolyte in comparative example 1
The charge-discharge performance test figure of ion battery.
Detailed description of the invention
For making those skilled in the art be more fully understood that technical scheme, knot below
Close the drawings and specific embodiments the present invention is described in further detail.
Embodiment 1
The present embodiment provides a kind of lithium ion battery with Si-C composite material as negative material
With electrolyte, including: lithium salts LiPF6, non-aqueous organic solvent EC, DEC and FEC(its
In, the mass ratio of EC, DEC and FEC is EC:DEC:FEC=6:3:1), film forming
Additive VC and TPFPB.Wherein, LiPF6The content that concentration is 1M, VC be institute
Stating the 2% of electrolyte gross weight, the content of TPFPB is the 5% of described electrolyte gross weight.
The compound method of this electrolyte is as follows: by lithium salts LiPF6It is dissolved in non-aqueous organic solvent
In the mixed solvent of EC, DEC and FEC, wherein, the quality of EC, DEC and FEC
Ratio is EC:DEC:FEC=6:3:1, LiPF6Concentration be 1M；Molten at this most again
Liquid adds film for additive VC, adds film for additive TPFPB, obtain electrolyte.
Wherein, the content of VC is the 2% of described electrolyte gross weight, and the content of TPFPB is institute
State the 5% of electrolyte gross weight.
In lithium ion battery, the formation of SEI film is to electrode material especially negative material
Vital impact can be produced, on the one hand, the formation of SEI film consume part lithium from
Son so that first charge-discharge irreversible capacity increases, and reduces the discharge and recharge of negative material
Efficiency；On the other hand, it is insoluble that SEI film has organic solvent, at organic electrolyte solution
Middle can stable existence, and solvent molecule can not be by this passivating film, it is thus possible to the most anti-
The only common embedding of solvent molecule, it is to avoid embed anticathode material altogether causes because of solvent molecule
Destruction, thus substantially increase cycle performance and the service life of negative pole.
Si-C composite material in the present embodiment is the lithium ion battery electrolysis of negative material
TPFPB in liquid, as the film for additive of SEI film, contributes on negative material surface
Formed and stablize complete SEI film.TPFPB not only has promotion and is formed on negative material
The effect of SEI film, TPFPB is relative to film for additive VC of the prior art simultaneously
More act on etc. having.The electronegativity of the fluorine connected on the phenyl in TPFPB is very strong,
Five fluorine have strong conjugation with phenyl so that pentafluorophenyl group becomes the strongest suction
Electronics base, and the electronics that attract around boron that pentafluorophenyl group is strong, so that boron is all
The cloud density enclosed is substantially reduced, and it is acid that such boron just has the strongest Lewis, and
Boron itself is electron-defect compound, and therefore, TPFPB is easy to and the inertia in SEI film
Material such as LiF, Li2O、Li2O2Deng reaction, make these several materials in the electrolytic solution molten
Xie Du increases, and this process discharges the lithium ion moved freely, thus adds electrolysis
The electrical conductivity of liquid, the circulation of such negative material and high rate performance all can be correspondingly improved.
TPFPB advantageously forms more stable SEI film, improves negative material surface molecules film
Stability, reduce solvent molecule common embedding.And the construction features of TPFPB determines
Himself more stable being not easy is decomposed, and improves the life-span of electrolyte.
Still further aspect, consumes part lithium ion in the forming process of SEI film, and by
TPFPB in electrolyte can discharge the lithium ion moved freely by SEI film,
Thus can balance out the part lithium ion consumed in the forming process of SEI film, thus drop
The first charge-discharge irreversible capacity of low negative material.
Silica-base material is poor as the cycle performance of negative material, such as, in the present embodiment
Si-C composite material, it is simply that because the bulk effect of Si-C composite material causes its outer formation
SEI film cracking efflorescence, so will the most again give birth to during charge and discharge cycles
Become SEI film, thus ceaselessly consume the lithium in the lithium salts in electrolyte.And in electrolyte
TPFPB can be discharged the lithium ion moved freely by SEI film, the most significantly
Decrease the loss of lithium in the lithium salts in electrolyte.
In sum, the TPFPB in electrolyte promotes to define more stable SEI film,
Lithium ion battery negative electrode active material silicon-carbon composite wood in charge and discharge process, on negative pole
The powder phenomenon-tion of the bulk effect of the silicon in material just weakens so that the efficiency for charge-discharge of battery
Improving, cycle performance is improved the most accordingly.
Si-C composite material in the present embodiment is the lithium ion battery electrolysis of negative material
With the addition of a small amount of VC in liquid, one is to promote film forming, and two is that the interpolation of VC is proved to can
To improve the cycle performance of battery.Therefore, in the electrolyte in this enforcement, preferably
Two kinds of film for additive of TPFPB and VC act on the formation promoting SEI film jointly.
Si-C composite material in the present embodiment is the lithium ion battery electrolysis of negative material
EC in liquid has resistant to elevated temperatures effect, owing to battery has in charge and discharge process relatively
High temperature, it is advantageous to non-aqueous organic molten as in the electrolyte in the present embodiment of EC
Agent.And DEC, DMC, EMC, FEC have good electrical conductivity, in the present embodiment
Preferably DEC, FEC and EC are collectively as non-aqueous organic solvent.
The present embodiment also provides for a kind of lithium ion battery, including above-mentioned electrolyte.
In the present embodiment, the negative electrode active material used in lithium ion battery process for preparation is
Si-C composite material, cell fabrication processes is as follows: by negative active core-shell material respectively with conduction
Agent acetylene black, binding agent PVDF mix according to mass ratio 80: 10: 10, use NMP
This mixture is modulated into slurry by (1-Methyl-2-Pyrrolidone), is coated uniformly on Copper Foil
On, 100 DEG C are vacuum dried 24 hours, prepared experimental cell pole piece.It is right with lithium sheet
Electrode, electrolyte is the above-mentioned electrolyte prepared, and barrier film is celgard2400 film,
It is assembled into CR2025 type button cell in being full of the glove box of argon gas atmosphere.
As it is shown in figure 1, the button cell that the electrolyte that the present embodiment is prepared is made is carried out
Charge-discharge performance is tested: charging and discharging currents is 0.2CA, and charging/discharging voltage is interval
Being 0.01～1.5V, after circulating 50 times, battery capacity conservation rate is about 87%.
Comparative example 1
This comparative example provides a kind of lithium ion battery with Si-C composite material as negative material
With electrolyte, including: lithium salts LiPF6, non-aqueous organic solvent EC, DEC and FEC(its
In, the mass ratio of EC, DEC and FEC is EC:DEC:FEC=6:3:1), film forming
Additive VC.Wherein, LiPF6The content that concentration is 1M, VC be described electrolyte
The 7% of gross weight.
The compound method of this electrolyte is as follows: by lithium salts LiPF6It is dissolved in non-aqueous organic solvent
In the mixed solvent of EC, DEC and FEC, wherein, the quality of EC, DEC and FEC
Ratio is EC:DEC:FEC=6:3:1, LiPF6Concentration be 1M；Molten at this most again
Liquid adds film for additive VC, obtains electrolyte.Wherein, the content of VC is described
The 7% of electrolyte gross weight.
As it is shown in figure 1, according to the method preparing button cell in embodiment 1, use this
Button cell made by the electrolyte of comparative example preparation, and this battery is carried out charge and discharge cycles
Performance test: charging and discharging currents is 0.2CA, charging/discharging voltage interval is 0.01～1.5V,
After circulating 50 times, battery capacity conservation rate is about 71%.
The lithium ion battery that in embodiment 1, the electrolyte of preparation is made is relative to this comparative example
The lithium ion battery made of electrolyte of preparation in 1 after charge and discharge cycles 50 times, battery
Capability retention higher, the cycle performance of battery is more preferable.
Embodiment 2
The present embodiment provides a kind of electrolysis of the lithium ion battery with silicon materials as negative material
Liquid, including: lithium salts LiClO4, non-aqueous organic solvent EC, DEC and DMC(wherein,
The mass ratio of EC, DEC and DMC is EC:DEC:DMC=4:4:2), film forming adds
Add agent VC and TPFPB.Wherein, LiClO4The content that concentration is 0.5M, VC be
The 2% of described electrolyte gross weight, the content of TPFPB is described electrolyte gross weight
2%。
The compound method of this electrolyte is as follows: by lithium salts LiClO4It is dissolved in non-aqueous organic solvent
In the mixed solvent of EC, DEC and DMC, wherein, the matter of EC, DEC and DMC
Amount ratio is EC:DEC:DMC=4:4:2, LiClO4Concentration be 0.5M；Exist the most again
This solution adds film for additive VC, adds film for additive TPFPB, obtain electricity
Solve liquid.Wherein, the content of VC is the 2% of described electrolyte gross weight, and TPFPB contains
Amount is the 2% of described electrolyte gross weight.
The present embodiment also provides for a kind of lithium ion battery, including above-mentioned electrolyte.
According to the method preparing button cell in embodiment 1, use the present embodiment preparation
Button cell made by electrolyte, and this battery is carried out charge-discharge performance test: fill
Discharge current is 0.2CA, and charging/discharging voltage interval is 0.01～1.5V, circulates 50 times
After, battery capacity conservation rate is about 79.4%.
Embodiment 3
The present embodiment provides a kind of lithium ion battery with Si-Cu alloy material as negative material
With electrolyte, including: lithium salts LiPF6And LiClO4, non-aqueous organic solvent EC, EMC
With DMC(wherein, the mass ratio of EC, EMC and DMC is EC:EMC:
DMC=4:3:3), film for additive VC, VEC and TPFPB.Wherein, LiPF6's
Concentration is 0.6M, LiClO4The content that concentration is 0.4M, VC be that described electrolyte is total
The 2% of weight, the content of VEC is the 1% of described electrolyte gross weight, and TPFPB contains
Amount is the 4% of described electrolyte gross weight.
The compound method of this electrolyte is as follows: by lithium salts LiPF6And LiClO4It is dissolved in non-aqueous
In the mixed solvent of organic solvent EC, EMC and DMC, wherein, EC, EMC and
The mass ratio of DMC is EC:EMC:DMC=4:3:3, LiPF6Concentration be 0.6M,
LiClO4Concentration be 0.4M；Film for additive VC is added the most again in this solution,
Add film for additive VEC, add film for additive TPFPB, obtain electrolyte.
Wherein, the content of VC is the 2% of described electrolyte gross weight, and the content of VC is described electricity
Solving the 1% of liquid gross weight, the content of TPFPB is the 4% of described electrolyte gross weight.
The present embodiment also provides for a kind of lithium ion battery, including above-mentioned electrolyte.
According to the method preparing button cell in embodiment 1, use the present embodiment preparation
Button cell made by electrolyte, and this battery is carried out charge-discharge performance test: fill
Discharge current is 0.2CA, and charging/discharging voltage interval is 0.01～1.5V, circulates 50 times
After, battery capacity conservation rate is about 80.7%.
Embodiment 4
The present embodiment provides a kind of lithium ion battery with Si-C composite material as negative material
With electrolyte, including: lithium salts LiB (C2O4)2, non-aqueous organic solvent EC and DMC
(wherein, the mass ratio of EC and DMC is EC:DMC=4:3), film for additive
1,3-PS and TPFPB.Wherein, LiB (C2O4)2Concentration be 0.8M, 1,3-PS
Content is the 4% of described electrolyte gross weight, and the content of TPFPB is described electrolyte gross weight
The 1% of amount.
The compound method of this electrolyte is as follows: by lithium salts LiB (C2O4)2It is dissolved in non-aqueous organic
In the mixed solvent of solvent EC and DMC, wherein, the mass ratio of EC and DMC is
EC:DMC=4:3, LiB (C2O4)2Concentration be 0.8M；The most again in this solution
Add film for additive 1,3-PS, add film for additive TPFPB, obtain electrolyte.
Wherein, the content of 1,3-PS is the 4% of described electrolyte gross weight, and the content of TPFPB is
The 1% of described electrolyte gross weight.
The present embodiment also provides for a kind of lithium ion battery, including above-mentioned electrolyte.
According to the method preparing button cell in embodiment 1, use the present embodiment preparation
Button cell made by electrolyte, and this battery is carried out charge-discharge performance test: fill
Discharge current is 0.2CA, and charging/discharging voltage interval is 0.01～1.5V, circulates 50 times
After, battery capacity conservation rate is about 85.3%.
Embodiment 5
The present embodiment provides a kind of lithium ion battery with Si-C composite material as negative material
With electrolyte, including: lithium salts LiB (C2O4)2And LiClO4, non-aqueous organic solvent EC,
Wherein, the mass ratio of EC, DEC and EMC is EC:DEC to DEC and EMC(:
EMC=2:2:4), film for additive TPFPB.Wherein, LiB (C2O4)2Concentration be
0.5M, LiClO4The content that concentration is 0.5M, TPFPB be described electrolyte gross weight
7%.
The compound method of this electrolyte is as follows: by lithium salts LiB (C2O4)2And LiClO4Molten
In the mixed solvent of non-aqueous organic solvent EC, DEC and EMC, wherein, EC,
The mass ratio of DEC and EMC is EC:DEC:EMC=2:2:4, LiB (C2O4)2's
Concentration is 0.5M, LiClO4Concentration be 0.5M；Film forming is added the most again in this solution
Additive TPFPB, obtains electrolyte.Wherein, the content of TPFPB is described electrolyte
The 7% of gross weight.
The present embodiment also provides for a kind of lithium ion battery, including above-mentioned electrolyte.
According to the method preparing button cell in embodiment 1, use the present embodiment preparation
Button cell made by electrolyte, and this battery is carried out charge-discharge performance test: fill
Discharge current is 0.2CA, and charging/discharging voltage interval is 0.01～1.5V, circulates 50 times
After, battery capacity conservation rate is about 83.5%.
Embodiment 6
The present embodiment provide a kind of with Si-C composite material and silicon materials the lithium as negative material
With electrolyte, (wherein, Si-C composite material with the mass ratio of silicon materials is ion battery
1:1), including lithium salts LiB (C2O4)2And LiPF6, non-aqueous organic solvent EC, FEC
With EMC(wherein, the mass ratio of EC, FEC and EMC is EC:FEC:
EMC=3:3:4), film for additive Isosorbide-5-Nitrae-BS and TPFPB.Wherein, LiB (C2O4)2
Concentration be 0.7M, LiPF6Concentration be 0.3M, the content of Isosorbide-5-Nitrae-BS is described electrolysis
The 3% of liquid gross weight, the content of TPFPB is the 3% of described electrolyte gross weight.
The compound method of this electrolyte is as follows: by lithium salts LiB (C2O4)2And LiPF6It is dissolved in
In the mixed solvent of non-aqueous organic solvent EC, FEC and EMC, wherein, EC, FEC
It is EC:FEC:EMC=3:3:4, LiB (C with the mass ratio of EMC2O4)2Concentration
For 0.7M, LiPF6Concentration be 0.3M；In this solution, add film forming the most again add
Agent Isosorbide-5-Nitrae-BS, adds film for additive TPFPB, obtains electrolyte.Wherein, Isosorbide-5-Nitrae-BS
Content is described electrolyte gross weight 3%, the content of TPFPB is that described electrolyte is total
The 3% of weight.
The present embodiment also provides for a kind of lithium ion battery, including above-mentioned electrolyte.
According to the method preparing button cell in embodiment 1, use the present embodiment preparation
Button cell made by electrolyte, and this battery is carried out charge-discharge performance test: fill
Discharge current is 0.2CA, and charging/discharging voltage interval is 0.01～1.5V, circulates 50 times
After, battery capacity conservation rate is about 79.6%.
Embodiment 7
The present embodiment provides a kind of lithium ion battery with silicon nickel alloy material as negative material
With electrolyte, including: lithium salts LiPF6, non-aqueous organic solvent EC, film for additive Isosorbide-5-Nitrae-BS
And TPFPB.Wherein, LiPF6Concentration be 1.2M, the content of Isosorbide-5-Nitrae-BS is described electricity
Solving the 5% of liquid gross weight, the content of TPFPB is the 4% of described electrolyte gross weight.
The compound method of this electrolyte is as follows: by lithium salts LiPF6It is dissolved in non-aqueous organic solvent
In EC, wherein, LiPF6Concentration be 1.2M；Film forming is added the most again in this solution
Additive Isosorbide-5-Nitrae-BS, adds film for additive TPFPB, obtains electrolyte.Wherein,
The content of Isosorbide-5-Nitrae-BS is the 5% of described electrolyte gross weight, and the content of TPFPB is described electricity
Solve the 4% of liquid gross weight.
The present embodiment also provides for a kind of lithium ion battery, including above-mentioned electrolyte.
According to the method preparing button cell in embodiment 1, use the present embodiment preparation
Button cell made by electrolyte, and this battery is carried out charge-discharge performance test: fill
Discharge current is 0.2CA, and charging/discharging voltage interval is 0.01～1.5V, circulates 50 times
After, battery capacity conservation rate is about 82.5%.
It is understood that the principle that embodiment of above is intended to be merely illustrative of the present
And the illustrative embodiments used, but the invention is not limited in this.For ability
For those of ordinary skill in territory, in the situation without departing from spirit and substance of the present invention
Under, various modification and improvement can be made, these modification and improvement are also considered as the present invention's
Protection domain.
Claims (5)
1. the electrolyte for lithium ion battery with silica-base material as negative material, bag
Include: lithium salts, non-aqueous organic solvent, film for additive, wherein, described non-aqueous organic molten
Agent includes ethylene carbonate, it is characterised in that described film for additive includes three (five fluorine
Phenyl) borine, the content of described three (pentafluorophenyl group) borine is described electrolyte gross weight
The 1%～7% of amount, described film for additive also includes that vinylene carbonate, ethylene carbonate are sub-
Ethyl ester, 1, in 3-sulfonic acid propiolactone, Isosorbide-5-Nitrae-sulfonic acid butyrolactone one or more, film forming add
The content of remaining film for additive in addition to described three (pentafluorophenyl group) borine in agent is
The 2%～5% of described electrolyte gross weight, described non-aqueous organic solvent also includes fluoro carbonic acid
Vinyl acetate.
Lithium-ion electric with silica-base material as negative material the most according to claim 1
Pond electrolyte, it is characterised in that described lithium salts is LiPF6、LiClO4、LiB(C2O4)2In one or more.
Lithium-ion electric with silica-base material as negative material the most according to claim 1
Pond electrolyte, it is characterised in that the concentration of described lithium salts is 0.5M～1.2M.
Lithium-ion electric with silica-base material as negative material the most according to claim 1
Pond electrolyte, it is characterised in that described silica-base material is silicon materials, silicon-carbon composite wood
One or more in material, aluminosilicate alloy material.
5. a lithium ion battery, it is characterised in that include that Claims 1 to 4 is any one
Electrolyte described in Xiang.
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