CN102694200A - Silicon-based negative lithium-ion battery and manufacturing method thereof - Google Patents
Silicon-based negative lithium-ion battery and manufacturing method thereof Download PDFInfo
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- CN102694200A CN102694200A CN2012101608180A CN201210160818A CN102694200A CN 102694200 A CN102694200 A CN 102694200A CN 2012101608180 A CN2012101608180 A CN 2012101608180A CN 201210160818 A CN201210160818 A CN 201210160818A CN 102694200 A CN102694200 A CN 102694200A
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- ion battery
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 54
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 53
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 45
- 239000010703 silicon Substances 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000011248 coating agent Substances 0.000 claims abstract description 78
- 238000000576 coating method Methods 0.000 claims abstract description 78
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 78
- 239000010439 graphite Substances 0.000 claims abstract description 71
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- 230000004913 activation Effects 0.000 claims abstract description 11
- 239000013543 active substance Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 15
- 239000011889 copper foil Substances 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 14
- 239000006257 cathode slurry Substances 0.000 claims description 12
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 11
- 239000010410 layer Substances 0.000 claims description 10
- 238000005096 rolling process Methods 0.000 claims description 10
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- 230000004888 barrier function Effects 0.000 claims description 6
- 239000011247 coating layer Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007770 graphite material Substances 0.000 claims description 5
- 239000010406 cathode material Substances 0.000 claims description 4
- 230000020411 cell activation Effects 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 3
- 229910015645 LiMn Inorganic materials 0.000 claims description 3
- 229910013733 LiCo Inorganic materials 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000016507 interphase Effects 0.000 abstract 1
- 239000007784 solid electrolyte Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 14
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000011149 active material Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 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 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 210000005069 ears Anatomy 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000011239 graphite-silicon composite material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910012742 LiNi0.5Co0.3Mn0.2O2 Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a silicon-based negative lithium-ion battery and a manufacturing method thereof. The silicon-based cathode lithium-ion battery comprises a positive plate, a negative plate, a diaphragm, and electrolyte, wherein the negative plate comprises a negative current collector and a negative active substance distributed on the negative current collector; and the negative active substance comprises a carbon-silicon compound material; an active substance coating in the negative plate comprises a graphite coating and a carbon-silicon negative coating to form the negative plate with a compound coating structure. Electrolyte containing a compound additive is added in the manufacturing process, and a multi-section charging activation method is adopted in the first-charging process. According to the invention, the manufacturing method is helpful for improving adhesive property and processability of the silicon-carbon compound negative electrode, enhancing the buffer capacity to volume change in a charging and discharging process, improving compatibility of the silicon-based negative electrode and the electrolyte, improving the formation and stability of an SEI (solid electrolyte interphase) membrane on the surface of the negative electrode, and improving the electrochemical performance of the silicon-based negative lithium-ion battery.
Description
Technical field
The present invention relates to a kind of lithium ion battery, especially relate to a kind of lithium ion battery that contains silicium cathode, the invention still further relates to the manufacturing approach of this silicon-based anode lithium ion battery.
Background technology
Lithium ion battery has advantages such as operating voltage height, specific energy is high and have extended cycle life, and has obtained in recent years developing rapidly.Along with mobile device develops to miniaturization and multifunction direction, simultaneously along with the fast development and the extensive use of electric automobile, demand high for energy, the lithium ion battery that has extended cycle life is very urgent.The main negative material graphite of present commercial Li-ion batteries, because theoretical capacity low (372mAh/g), high-rate charge-discharge capability is poor, has limited the further raising of lithium ion battery energy.
Silicon has the highest theoretical specific capacity (4200mAh g
-1) and lower take off the lithium current potential (<0.5V), become one of lithium ion battery negative material of the most potential replacement graphite.But in charge and discharge process, huge change in volume can take place in silicon, causes the material efflorescence, peel off, lose and electrically contact, and capacity attenuation is very fast.In order to reduce the bulk effect of silicon materials, people have attempted several different methods, comprise the particle diameter that reduces silicon materials; Silicon is processed porous material; Reduce the dimension of silicon materials; Preparation Si-C composite material etc.The volumetric expansion that these methods have perhaps suppressed silicon materials has perhaps improved electrically contacting between the particle, thereby has improved the cyclical stability and the first charge-discharge efficiency of silicon-based anode to a certain extent.
But because silicon-based anode and the greatest differences of conventional carbon negative pole on structure and performance, conventional method prepares the silicon-based anode lithium ion battery and has a series of problems: crisp like bad adhesion, pole piece, and traditional electrolysis liquid phase capacitive is poor, cycle performance difference etc.Therefore, research and development are significant with the lithium ion battery manufacturing process that silicon-based anode adapts.
Summary of the invention
The caking property that first technical problem to be solved by this invention provides a kind of negative material and collector is high, the pliability of negative plate is good, the good silicon-based anode lithium ion battery of compatibility chemical property good and battery of negative pole and electrolyte.
Second technical problem to be solved by this invention provides a kind of method of making this silicon-based anode lithium ion battery.
In order to solve above-mentioned second technical problem; Silicon-based anode lithium ion battery provided by the invention; Comprise: positive plate, negative plate, barrier film; And electrolyte, positive plate comprises plus plate current-collecting body and is distributed in the positive active material on the plus plate current-collecting body that negative plate comprises negative current collector and is distributed in the negative electrode active material on the negative current collector; Described negative electrode active material is the coating layer of active substance that contains Si-C composite material that is located on the described negative plate, and described coating layer of active substance is the composite multi-layer structure that comprises graphite cathode coating and silicon-carbon cathode coating.
The composite multi-layer structure of described graphite cathode coating and silicon-carbon cathode coating comprises following several kinds of forms: graphite/Si-C composite material, Si-C composite material/graphite or graphite/Si-C composite material/graphite.
Described graphite cathode coating comprises graphite, binding agent and the additive of average grain diameter 3-6 μ m, and wherein content of graphite is 90-96%; Described silicon-carbon cathode coating comprises Si-C composite material, binding agent and additive.
The thickness of described graphite cathode coating is 5-30 μ m, and described silicon-carbon cathode coating layer thickness is 30-100 μ m.
Described positive active material is transition metal embedding lithium oxide or phosphate cathode material LiCoO
2, LiMn
2O
4, LiFePO
4, LiCo
1-x-yNi
xMn
yO
2In one or more, wherein, x, y, x+y＜1.
Be 1%～3% the vinylene carbonate (VC) except adding volume ratio in the described electrolyte, also add volume ratio and be 2%～4% vinylethylene carbonate (VEC), in the methane-disulfonic acid methylene ester (MMDS) one or both.
In order to solve above-mentioned second technical problem, the manufacturing approach of silicon-based anode lithium ion battery provided by the invention comprises the positive plate preparation; The negative plate preparation; Assembling, filling electrolyte, cell activation step; The step of described negative plate preparation is: respectively graphite, binding agent and additive are mixed with the graphite cathode slurry, Si-C composite material, binding agent and additive are mixed with the silicon-carbon cathode slurry; Apply by one of following 3 kinds of modes: (1) applies one deck graphite cathode coating, oven dry at the negative current collector copper foil surface; Then apply one deck silicon-carbon cathode coating, oven dry at the graphite cathode coating surface; (2) apply one deck silicon-carbon cathode coating, oven dry at the negative current collector copper foil surface; Apply one deck graphite cathode coating again at the silicon-carbon cathode coating surface then, oven dry; (3) apply one deck graphite cathode coating, oven dry at the negative current collector copper foil surface; Then apply one deck silicon-carbon cathode coating, oven dry at the graphite cathode coating surface; Apply one deck graphite cathode coating again at the silicon-carbon cathode coating surface then, oven dry; The diaphragm that above-mentioned several kinds of application pattern obtain through rolling, cut and obtain composite multi-layer structure negative plate.
It is the multistage electricizing activation of little electric current that described cell activation step adopts first latter end.
Described multistage electricizing activation is meant: adopting first latter end during the lithium ion battery initial charge is the multistage electricizing activation of little electric current, first 0.05C constant current charge 1 hour, and the 0.2C constant current charge is to 4.0V again, and last 0.05C charges to 4.2V and accomplishes initial charge.
Adopt the silicon-based anode lithium ion battery and the manufacturing approach thereof of technique scheme, with respect to prior art, the present invention has following good effect:
(1) because the specific area of carbon-silicon composite material is bigger, generally relatively poor with the adhesive property of collector.The present invention applies one deck equadag coating earlier in the negative pole currect collecting surface, and then carbon-coated silicon composite cathode coating, helps improving the adhesive property of carbon silicium cathode coating.
(2) the present invention applies one deck equadag coating again after carbon-coated silicon composite cathode coating, can improve the compatibility of negative pole coating and electrolyte.
(3) the present invention preferably adopts " graphite/Si-C composite material/graphite " composite coating structure, helps improving the caking property of silicon-based anode and collector, and with the compatibility of electrolyte, and " expansion-contraction " bulk effect of silicon in the buffering charging process.
(4) the present invention adopts equadag coating and silicon-carbon composite cathode coating, and in cathode size, adds scale graphite, has improved the pliability and the processing characteristics of silicon-based anode.
(5) the present invention adopts the syllogic charging when initial charge, and promptly the first end stage is all adopted little electric current, makes graphite and carbon silicon composite cathode material surface all can form well behaved fine and close SEI film.
(6) the present invention adds compound additive in electrolyte, has improved the SEI film of graphite and carbon silicon composite cathode material.
By the way, make the energy density of the silicon-based anode lithium ion battery among the present invention exceed more than 20% than the energy density of conventional graphite negative electrode lithium ion battery, it is suitable with the graphite cathode lithium ion battery that cycle performance reaches.
Description of drawings
Fig. 1 silicon-based anode composite coating structure sketch map
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described further.
Embodiment 1:
With LiNi
0.5Co
0.3Mn
0.2O
2As active substance of lithium ion battery anode, be hybridly prepared into LiNi with binding agent, conductive agent, additive, solvent etc.
0.5Co
0.3Mn
0.2O
2Anode sizing agent, is cut at coated then, dry, rolling, obtains positive plate.
With average grain diameter is that the graphite of 5 μ m is as lithium ion battery negative pole active materials; With binding agent Kynoar, Super P conductive carbon, additive scale graphite be 91: 5: 2 by mass ratio: 2, be hybridly prepared into the graphite cathode slurry with solvent N-methyl pyrrolidone etc.Simultaneously; With Si-C composite material as lithium ion battery negative pole active materials; With Kynoar, Super P conductive carbon, additive scale graphite be 88: 7: 2 by mass ratio: 3, be hybridly prepared into the silicon-carbon composite cathode slurry with solvent N-methyl pyrrolidone etc.
Apply the thick graphite cathode coating of one deck 10 μ m at the negative current collector copper foil surface, oven dry; Then apply the thick silicon-carbon cathode coating of one deck 50 μ m, oven dry at the graphite cathode coating surface; Apply the thick graphite cathode coating of one deck 10 μ m again at the silicon-carbon cathode coating surface then, oven dry; And then, obtain silicon-based anode as shown in Figure 1 in the another side of Copper Foil coated graphite negative pole coating, silicon-carbon cathode coating, graphite cathode coating successively as stated above.This Figure illustrates the cross section structure of silicon-based anode, wherein 1 is copper foil of affluxion body, and 2 is the graphite cathode coating, and 3 is the silicon-carbon cathode coating.The gained cathode membrane through rolling, cut and obtain composite multi-layer structure negative plate.
Aluminium pole ears is welded on the positive plate, and the nickel lug is welded on the negative plate, with the positive plate that has welded lug; Negative plate and barrier film mode through reeling; The battery that forms is assembled in the aluminum hull, and with the mode of laser welding battery cover board and housing is welded together.The battery size of making is 523450 (thickness 5.2mm, width 34mm, length 50mm), nominal capacity 1400mAh.
To in the battery of operations such as the degassing dewaters, injecting electrolyte, concentration of electrolyte is 1mol/L, and lithium salts is lithium hexafluoro phosphate (LiPF
6); Mixture with ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) is a solvent; Wherein the ratio of each carbonic ester is DMC: EMC: EC=1: 1: 1, in electrolyte, add the vinylene carbonate (VC) and 3% vinylethylene carbonate (VEC) of 2% (volume ratio) again.
Adopt the multistage electricizing activation after the fluid injection during according to initial charge, earlier with 70mA (0.05C) constant current charge 1 hour, again with 280mA (0.2C) constant current charge to 4.0V, charge to 4.2V with 70mA (0.05C) at last and accomplish initial charge; Carry out the compressed steel pearl then in a conventional manner and discharge and recharge obtaining the silicon-based anode lithium ion battery.
At room temperature with the current discharge of 700mA (0.5C), initial discharge capacity is 1430mAh to gained silicon-based anode lithium ion battery, is 83% with the capability retention after the 0.5C multiplying power circulation 500 times.
Embodiment 2:
With LiCoO
2As active substance of lithium ion battery anode, be hybridly prepared into LiCoO with binding agent, conductive agent, additive, solvent etc.
2Anode sizing agent, is cut at coated then, dry, rolling, obtains positive plate.
With average grain diameter be the graphite of 3 μ m as lithium ion battery negative pole active materials, with water system binding agent (SBR supernatant liquid and CMC mixture), additive scale graphite be 96: 2.5: 1 by mass ratio, be hybridly prepared into the graphite cathode slurry with deionized water etc.Simultaneously, as lithium ion battery negative pole active materials, water system binding agent (SBR supernatant liquid and CMC mixture), additive scale graphite are 93: 5: 2 by mass ratio with Si-C composite material, are hybridly prepared into the silicon-carbon composite cathode slurry with deionized water etc.
Apply the thick graphite cathode coating of one deck 5 μ m at the negative current collector copper foil surface, oven dry; Then apply the thick silicon-carbon cathode coating of one deck 95 μ m, oven dry at the graphite cathode coating surface; And then in the another side of Copper Foil coated graphite negative pole coating, silicon-carbon cathode coating successively as stated above.The gained cathode membrane through rolling, cut and obtain composite multi-layer structure negative plate.
Aluminium pole ears is welded on the positive plate, and the nickel lug is welded on the negative plate, with the positive plate that has welded lug; Negative plate and barrier film mode through reeling; The battery that forms is assembled in the aluminum hull, and with the mode of laser welding battery cover board and housing is welded together.The battery size of making is 523450 (thickness 5.2mm, width 34mm, length 50mm), nominal capacity 1400mAh.
To in the battery of operations such as the degassing dewaters, injecting electrolyte, concentration of electrolyte is 1mol/L, and lithium salts is lithium hexafluoro phosphate (LiPF
6); Mixture with ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) is a solvent; Wherein the ratio of each carbonic ester is DMC: EMC: EC=1: 1: 1, in electrolyte, add the vinylene carbonate (VC) and the 2% methane-disulfonic acid methylene ester (MMDS) of 3% (volume ratio) again.
Adopt the multistage electricizing activation after the fluid injection during according to initial charge, earlier with 70mA (0.05C) constant current charge 1 hour, again with 280mA (0.2C) constant current charge to 4.0V, charge to 4.2V with 70mA (0.05C) at last and accomplish initial charge; Carry out the compressed steel pearl then in a conventional manner and discharge and recharge obtaining the silicon-based anode lithium ion battery.
At room temperature with the current discharge of 700mA (0.5C), initial discharge capacity is 1460mAh to gained silicon-based anode lithium ion battery, is 84% with the capability retention after the 0.5C multiplying power circulation 500 times.
Embodiment 3:
With LiNi
0.8Co
0.1Mn
0.1O
2And LiMn
2O
4As active substance of lithium ion battery anode, be hybridly prepared into anode sizing agent with binding agent, conductive agent, additive, solvent etc., coated then, dry, rolling, cut, obtain positive plate.
With average grain diameter is that the graphite of 6 μ m is as lithium ion battery negative pole active materials; With Kynoar, Super P conductive carbon, additive scale graphite be 91: 5: 2 by mass ratio: 2, be hybridly prepared into the graphite cathode slurry with solvent N-methyl pyrrolidone etc.Simultaneously; With Si-C composite material as lithium ion battery negative pole active materials; With Kynoar, Super P conductive carbon, additive scale graphite be 88: 7: 2 by mass ratio: 3, be hybridly prepared into the silicon-carbon composite cathode slurry with solvent N-methyl pyrrolidone etc.
Apply the thick graphite cathode coating of one deck 30 μ m at the negative current collector copper foil surface, oven dry; Then apply the thick silicon-carbon cathode coating of one deck 30 μ m, oven dry at the graphite cathode coating surface; Apply the thick graphite cathode coating of one deck 10 μ m again at the silicon-carbon cathode coating surface then, oven dry; And then in the another side of Copper Foil coated graphite negative pole coating, silicon-carbon cathode coating, graphite cathode coating successively as stated above, the gained cathode membrane through rolling, cut and obtain composite multi-layer structure negative plate.
Aluminium pole ears is welded on the positive plate, and the nickel lug is welded on the negative plate, with the positive plate that has welded lug; Negative plate and barrier film mode through reeling; The battery that forms is assembled in the aluminum hull, and with the mode of laser welding battery cover board and housing is welded together.The battery size of making is 523450 (thickness 5.2mm, width 34mm, length 50mm), nominal capacity 1400mAh.
To in the battery of operations such as the degassing dewaters, injecting electrolyte, concentration of electrolyte is 1mol/L, and lithium salts is lithium hexafluoro phosphate (LiPF
6); Mixture with ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) is a solvent; Wherein the ratio of each carbonic ester is DMC: EMC: EC=1: 1: 1, in electrolyte, add the vinylene carbonate (VC) and 3% vinylethylene carbonate (VEC) of 2% (volume ratio) again.
Adopt the multistage electricizing activation after the fluid injection during according to initial charge, earlier with 70mA (0.05C) constant current charge 1 hour, again with 280mA (0.2C) constant current charge to 4.0V, charge to 4.2V with 70mA (0.05C) at last and accomplish initial charge; Carry out the compressed steel pearl then in a conventional manner and discharge and recharge obtaining the silicon-based anode lithium ion battery.
At room temperature with the current discharge of 700mA (0.5C), initial discharge capacity is 1480mAh to gained silicon-based anode lithium ion battery, is 82% with the capability retention after the 0.5C multiplying power circulation 500 times.
Embodiment 4:
With LiNi
1/3Co
1/3Mn
1/3O
2And LiFePO
4As active substance of lithium ion battery anode, be hybridly prepared into anode sizing agent with binding agent, conductive agent, additive, solvent etc., coated then, dry, rolling, cut, obtain positive plate.
With average grain diameter is that the graphite of 6 μ m is as lithium ion battery negative pole active materials; With Kynoar, Super P conductive carbon, additive scale graphite be 91: 5: 2 by mass ratio: 2, be hybridly prepared into the graphite cathode slurry with solvent N-methyl pyrrolidone etc.Simultaneously; With Si-C composite material as lithium ion battery negative pole active materials; With Kynoar, Super P conductive carbon, additive scale graphite be 88: 7: 2 by mass ratio: 3, be hybridly prepared into the silicon-carbon composite cathode slurry with solvent N-methyl pyrrolidone etc.
Apply the thick silicon-carbon cathode coating of one deck 50 μ m at the negative current collector copper foil surface, oven dry; Apply the thick graphite cathode coating of one deck 20 μ m again at the silicon-carbon cathode coating surface then, oven dry; And then apply silicon-carbon cathode coating, graphite cathode coating as stated above successively at the another side of Copper Foil, the gained cathode membrane through rolling, cut and obtain composite multi-layer structure negative plate.
Aluminium pole ears is welded on the positive plate, and the nickel lug is welded on the negative plate, with the positive plate that has welded lug; Negative plate and barrier film mode through reeling; The battery that forms is assembled in the aluminum hull, and with the mode of laser welding battery cover board and housing is welded together.The battery size of making is 523450 (thickness 5.2mm, width 34mm, length 50mm), nominal capacity 1400mAh.
To in the battery of operations such as the degassing dewaters, injecting electrolyte, concentration of electrolyte is 1mol/L, and lithium salts is lithium hexafluoro phosphate (LiPF
6); Mixture with ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) is a solvent; Wherein the ratio of each carbonic ester is DMC: EMC: EC=1: 1: 1, in electrolyte, add the vinylene carbonate (VC) and 4% vinylethylene carbonate (VEC) of 1% (volume ratio) again.
Adopt the multistage electricizing activation after the fluid injection during according to initial charge, earlier with 70mA (0.05C) constant current charge 1 hour, again with 280mA (0.2C) constant current charge to 4.0V, charge to 4.2V with 70mA (0.05C) at last and accomplish initial charge; Carry out the compressed steel pearl then in a conventional manner and discharge and recharge obtaining the silicon-based anode lithium ion battery.
At room temperature with the current discharge of 700mA (0.5C), initial discharge capacity is 1415mAh to gained silicon-based anode lithium ion battery, is 85% with the capability retention after the 0.5C multiplying power circulation 500 times.
Claims (9)
1. silicon-based anode lithium ion battery; Comprise: positive plate, negative plate, barrier film; And electrolyte; Positive plate comprises plus plate current-collecting body and is distributed in the positive active material on the plus plate current-collecting body; Negative plate comprise negative current collector be distributed in the negative electrode active material on the negative current collector, it is characterized in that: described negative electrode active material is the coating layer of active substance that contains Si-C composite material that is located on the described negative plate, described coating layer of active substance is the composite multi-layer structure that comprises graphite cathode coating and silicon-carbon cathode coating.
2. silicon-based anode lithium ion battery according to claim 1 is characterized in that: the composite multi-layer structure of described graphite cathode coating and silicon-carbon cathode coating comprises following several kinds of forms: graphite/Si-C composite material, Si-C composite material/graphite or graphite/Si-C composite material/graphite.
3. silicon-based anode lithium ion battery according to claim 1 and 2 is characterized in that: described graphite cathode coating comprises graphite, binding agent and the additive of average grain diameter 3-6 μ m, and wherein content of graphite is 90-96%; Described silicon-carbon cathode coating comprises Si-C composite material, binding agent and additive.
4. silicon-based anode lithium ion battery according to claim 1 and 2 is characterized in that: the thickness of described graphite cathode coating is 5-30 μ m, and described silicon-carbon cathode coating layer thickness is 30-100 μ m.
5. silicon-based anode lithium ion battery according to claim 1 and 2 is characterized in that: described positive active material is transition metal embedding lithium oxide or phosphate cathode material LiCoO
2, LiMn
2O
4, LiFePO
4, LiCo
1-x-yNi
xMn
yO
2In one or more, wherein, x, y, x+y＜1.
6. silicon-based anode lithium ion battery according to claim 1 and 2; It is characterized in that: be 1%～3% the vinylene carbonate except adding volume ratio in the described electrolyte, also add volume ratio and be 2%～4% vinylethylene carbonate, in the methane-disulfonic acid methylene ester one or both.
7. make the method for the described silicon-based anode lithium ion battery of claim 1; Comprise the positive plate preparation, negative plate preparation, assembling; Filling electrolyte; The cell activation step is characterized in that: the step of described negative plate preparation is: respectively graphite, binding agent and additive are mixed with the graphite cathode slurry, Si-C composite material, binding agent and additive are mixed with the silicon-carbon cathode slurry; Apply by one of following 3 kinds of modes: (1) applies one deck graphite cathode coating, oven dry at the negative current collector copper foil surface; Then apply one deck silicon-carbon cathode coating, oven dry at the graphite cathode coating surface; (2) apply one deck silicon-carbon cathode coating, oven dry at the negative current collector copper foil surface; Apply one deck graphite cathode coating again at the silicon-carbon cathode coating surface then, oven dry; (3) apply one deck graphite cathode coating, oven dry at the negative current collector copper foil surface; Then apply one deck silicon-carbon cathode coating, oven dry at the graphite cathode coating surface; Apply one deck graphite cathode coating again at the silicon-carbon cathode coating surface then, oven dry; The diaphragm that above-mentioned several kinds of application pattern obtain through rolling, cut and obtain composite multi-layer structure negative plate.
8. the method for manufacturing silicon-based anode lithium ion battery according to claim 7 is characterized in that: it is the multistage electricizing activation of little electric current that described cell activation step adopts first latter end.
9. the method for manufacturing silicon-based anode lithium ion battery according to claim 8; It is characterized in that: described multistage electricizing activation is meant: adopting first latter end during the lithium ion battery initial charge is the multistage electricizing activation of little electric current; The 0.05C of elder generation constant current charge 1 hour; The 0.2C constant current charge is to 4.0V again, and last 0.05C charges to 4.2V and accomplishes initial charge.
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