CN102694200B - 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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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 48
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 47
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 37
- 239000010703 silicon Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 75
- 239000011248 coating agent Substances 0.000 claims abstract description 74
- 238000000576 coating method Methods 0.000 claims abstract description 74
- 239000010439 graphite Substances 0.000 claims abstract description 69
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000013543 active substance Substances 0.000 claims abstract description 12
- 230000004913 activation Effects 0.000 claims abstract description 11
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 27
- 239000011230 binding agent Substances 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 239000011889 copper foil Substances 0.000 claims description 13
- 239000006257 cathode slurry Substances 0.000 claims description 12
- 239000002131 composite material 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
- 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
- 239000011247 coating layer Substances 0.000 claims description 7
- 230000004888 barrier function Effects 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
- 238000004458 analytical method Methods 0.000 claims description 5
- 239000007770 graphite material Substances 0.000 claims description 5
- 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 3
- 238000002360 preparation method Methods 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 5
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 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
- 229910052799 carbon Inorganic materials 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
- 238000003466 welding Methods 0.000 description 8
- 229910052744 lithium Inorganic materials 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
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 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
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000006258 conductive agent Substances 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
- 239000010406 cathode material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 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
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 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
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011239 graphite-silicon composite material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
-
- 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 containing silicium cathode, the invention still further relates to the manufacture method of this silicon-based anode lithium ion battery.
Background technology
Lithium ion battery has the advantages such as operating voltage is high, specific energy is high and have extended cycle life, and obtains in recent years and develops rapidly.Along with mobile device is to miniaturized and multifunction future development, while along with the fast development of electric automobile and extensive use, the demand of lithium ion battery that is high for energy, that have extended cycle life is very urgent.The main negative material graphite of current commercial Li-ion batteries, due to theoretical capacity low (372mAh/g), high-rate charge-discharge capability is poor, limits the further raising of lithium ion battery energy.
Silicon has the highest theoretical specific capacity (4200mAh g
-1) and lower de-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, can there is huge change in volume in silicon, causes material efflorescence, peels off, loses electrical contact, and capacity attenuation is very fast.In order to reduce the bulk effect of silicon materials, people have attempted multiple method, comprise the particle diameter reducing silicon materials; Silicon is made porous material; Reduce the dimension of silicon materials; Prepare Si-C composite material etc.These methods or inhibit the volumetric expansion of silicon materials, or improve the electrical contact between particle, thus improve cyclical stability and the first charge-discharge efficiency of silicon-based anode to a certain extent.
But, the greatest differences on Structure and Properties due to silicon-based anode and conventional carbon negative pole, conventional method is prepared silicon-based anode lithium ion battery and be there is series of problems: as crisp in bad adhesion, pole piece, with traditional electrolyte poor compatibility, cycle performance difference etc.Therefore, the lithium ion battery manufacture process adapted with silicon-based anode is researched and developed significant.
Summary of the invention
The silicon-based anode lithium ion battery that the caking property that first technical problem to be solved by this invention is to provide a kind of negative material and collector pliability that is high, negative plate is good, the compatibility chemical property that is good and battery of negative pole and electrolyte is good.
Second technical problem to be solved by this invention is to provide a kind of method manufacturing 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 plus plate current-collecting body, negative plate comprises negative current collector and is distributed in the negative electrode active material on negative current collector, described negative electrode active material is the coating layer of active substance containing Si-C composite material be located on described negative plate, described coating layer of active substance is the composite layered structure comprising graphite cathode coating and silicon-carbon cathode coating.
Described graphite cathode coating and the composite layered structure of silicon-carbon cathode coating comprise following several form: 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 μm, 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 μm, and described silicon-carbon cathode coating layer thickness is 30-100 μm.
Described positive active material is the embedding oxidate for lithium of transition metal 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.
Being except the vinylene carbonate (VC) of 1% ~ 3% except adding volume ratio in described electrolyte, also adding vinylethylene carbonate (VEC), one or both in methane-disulfonic acid methylene ester (MMDS) that volume ratio is 2% ~ 4%.
In order to solve above-mentioned second technical problem, the manufacture method of silicon-based anode lithium ion battery provided by the invention, comprise positive plate preparation, prepared by negative plate, assembling, filling electrolyte, cell activation step, step prepared by described negative plate is: respectively graphite, binding agent and additive are mixed with graphite cathode slurry, and Si-C composite material, binding agent and additive are mixed with silicon-carbon cathode slurry; Apply by one of following 3 kinds of modes: (1) applies one deck graphite cathode coating at negative current collector copper foil surface, dry; Then apply one deck silicon-carbon cathode coating at graphite cathode coating surface, dry; (2) apply one deck silicon-carbon cathode coating at negative current collector copper foil surface, dry; Then apply one deck graphite cathode coating again at silicon-carbon cathode coating surface, dry; (3) apply one deck graphite cathode coating at negative current collector copper foil surface, dry; Then apply one deck silicon-carbon cathode coating at graphite cathode coating surface, dry; Then apply one deck graphite cathode coating again at silicon-carbon cathode coating surface, dry; The diaphragm that above-mentioned several application pattern obtains through rolling, cut and obtain composite layered structure negative plate.
Described cell activation step employing first and last section is the multistage electricizing activation of small area analysis.
Described multistage electricizing activation refers to: during lithium ion battery initial charge, employing first and last section is the multistage electricizing activation of small area analysis, first 0.05C constant current charge 1 hour, then 0.2C constant current charge is to 4.0V, and last 0.05C charges to 4.2V and completes initial charge.
Adopt silicon-based anode lithium ion battery and the manufacture method thereof of technique scheme, relative to prior art, the present invention has following good effect:
(1) specific area due to carbon-silicon composite material is larger, poor with the adhesive property of collector under normal circumstances.The present invention first applies one deck equadag coating in negative pole currect collecting surface, and then coating carbon silicon composite cathode coating, is conducive to the adhesive property improving carbon silicium cathode coating.
(2) the present invention is after coating carbon silicon composite cathode coating, then applies one deck equadag 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, is conducive to the caking property improving silicon-based anode and collector, and with the compatibility of electrolyte, and cushion " expansion-contraction " bulk effect of silicon in charging process.
(4) the present invention adopts equadag coating and silicon-carbon composite cathode coating, and adds scale graphite in cathode size, improves pliability and the processing characteristics of silicon-based anode.
(5) the present invention adopts three stage charging system when initial charge, and namely the first and last stage all adopts small area analysis, makes graphite and the carbon silicon composite cathode material surface fine and close SEI film that all energy forming property is good.
(6) the present invention adds compound additive in the electrolytic solution, improves 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 in the present invention exceed more than 20% than the energy density of conventional graphite negative electrode lithium ion battery, cycle performance reaches suitable with graphite cathode lithium ion battery.
Accompanying drawing explanation
Fig. 1 silicon-based anode composite coating structure schematic diagram
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
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, then coated, dry, rolling, cut, obtain positive plate.
Be that the graphite of 5 μm is as lithium ion battery negative pole active materials using average grain diameter, be 91: 5: 2: 2 in mass ratio with binding agent Kynoar, Super P conductive carbon, additive scale graphite, be hybridly prepared into graphite cathode slurry with solvent N-methyl pyrilidone etc.Simultaneously, using Si-C composite material as lithium ion battery negative pole active materials, be 88: 7: 2: 3 in mass ratio with Kynoar, Super P conductive carbon, additive scale graphite, be hybridly prepared into silicon-carbon composite cathode slurry with solvent N-methyl pyrilidone etc.
Apply the thick graphite cathode coating of one deck 10 μm at negative current collector copper foil surface, dry; Then apply the thick silicon-carbon cathode coating of one deck 50 μm at graphite cathode coating surface, dry; Then apply the thick graphite cathode coating of one deck 10 μm again at silicon-carbon cathode coating surface, dry; And then in another side coated graphite negative pole coating, silicon-carbon cathode coating, the graphite cathode coating successively as stated above of Copper Foil, obtain silicon-based anode as shown in Figure 1.This Figure illustrates the cross section structure of silicon-based anode, wherein 1 is copper foil of affluxion body, and 2 is graphite cathode coating, and 3 is silicon-carbon cathode coating.Gained cathode membrane through rolling, cut and obtain composite layered structure negative plate.
Be welded on by aluminium pole ears on positive plate, nickel tab welding, on negative plate, will weld the positive plate of lug, negative plate and the mode of barrier film by reeling, the battery formed, is assembled in aluminum hull, and with the mode of laser welding by battery cover board together with case weld.The battery size made is 523450(thickness 5.2mm, width 34mm, length 50mm), nominal capacity 1400mAh.
In the battery through the degassed operation such as to dewater, inject electrolyte, concentration of electrolyte is 1mol/L, and lithium salts is lithium hexafluoro phosphate (LiPF
6), with the mixture of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) for solvent, wherein the ratio of each carbonic ester is DMC: EMC: EC=1: 1: 1, then adds 2%(volume ratio in the electrolytic solution) vinylene carbonate (VC) and 3% vinylethylene carbonate (VEC).
Multistage electricizing activation is adopted according to during initial charge after fluid injection, first with 70mA (0.05C) constant current charge 1 hour, again with 280mA (0.2C) constant current charge to 4.0V, finally charge to 4.2V with 70mA (0.05C) and complete initial charge; Then compressed steel pearl is carried out in a conventional manner and discharge and recharge obtains silicon-based anode lithium ion battery.
Gained silicon-based anode lithium ion battery is at room temperature with 700mA(0.5C) current discharge, initial discharge capacity is 1430mAh, with the capability retention after 0.5C circulation 500 times for 83%.
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, then coated, dry, rolling, cut, obtain positive plate.
Using average grain diameter be the graphite of 3 μm as lithium ion battery negative pole active materials, be 96: 2.5: 1 in mass ratio with water-based binder (SBR supernatant liquid and CMC mixture), additive scale graphite, be hybridly prepared into graphite cathode slurry with deionized water etc.Meanwhile, using Si-C composite material as lithium ion battery negative pole active materials, water-based binder (SBR supernatant liquid and CMC mixture), additive scale graphite are 93: 5: 2 in mass ratio, are hybridly prepared into silicon-carbon composite cathode slurry with deionized water etc.
Apply the thick graphite cathode coating of one deck 5 μm at negative current collector copper foil surface, dry; Then apply the thick silicon-carbon cathode coating of one deck 95 μm at graphite cathode coating surface, dry; And then in another side coated graphite negative pole coating, the silicon-carbon cathode coating successively as stated above of Copper Foil.Gained cathode membrane through rolling, cut and obtain composite layered structure negative plate.
Be welded on by aluminium pole ears on positive plate, nickel tab welding, on negative plate, will weld the positive plate of lug, negative plate and the mode of barrier film by reeling, the battery formed, is assembled in aluminum hull, and with the mode of laser welding by battery cover board together with case weld.The battery size made is 523450(thickness 5.2mm, width 34mm, length 50mm), nominal capacity 1400mAh.
In the battery through the degassed operation such as to dewater, inject electrolyte, concentration of electrolyte is 1mol/L, and lithium salts is lithium hexafluoro phosphate (LiPF
6), with the mixture of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) for solvent, wherein the ratio of each carbonic ester is DMC: EMC: EC=1: 1: 1, then adds 3%(volume ratio in the electrolytic solution) vinylene carbonate (VC) and 2% methane-disulfonic acid methylene ester (MMDS).
Multistage electricizing activation is adopted according to during initial charge after fluid injection, first with 70mA (0.05C) constant current charge 1 hour, again with 280mA (0.2C) constant current charge to 4.0V, finally charge to 4.2V with 70mA (0.05C) and complete initial charge; Then compressed steel pearl is carried out in a conventional manner and discharge and recharge obtains silicon-based anode lithium ion battery.
Gained silicon-based anode lithium ion battery is at room temperature with 700mA(0.5C) current discharge, initial discharge capacity is 1460mAh, with the capability retention after 0.5C circulation 500 times for 84%.
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., then coated, dry, rolling, cut, obtain positive plate.
Be that the graphite of 6 μm is as lithium ion battery negative pole active materials using average grain diameter, be 91: 5: 2: 2 in mass ratio with Kynoar, Super P conductive carbon, additive scale graphite, be hybridly prepared into graphite cathode slurry with solvent N-methyl pyrilidone etc.Simultaneously, using Si-C composite material as lithium ion battery negative pole active materials, be 88: 7: 2: 3 in mass ratio with Kynoar, Super P conductive carbon, additive scale graphite, be hybridly prepared into silicon-carbon composite cathode slurry with solvent N-methyl pyrilidone etc.
Apply the thick graphite cathode coating of one deck 30 μm at negative current collector copper foil surface, dry; Then apply the thick silicon-carbon cathode coating of one deck 30 μm at graphite cathode coating surface, dry; Then apply the thick graphite cathode coating of one deck 10 μm again at silicon-carbon cathode coating surface, dry; And then in another side coated graphite negative pole coating, silicon-carbon cathode coating, the graphite cathode coating successively as stated above of Copper Foil, gained cathode membrane through rolling, cut and obtain composite layered structure negative plate.
Be welded on by aluminium pole ears on positive plate, nickel tab welding, on negative plate, will weld the positive plate of lug, negative plate and the mode of barrier film by reeling, the battery formed, is assembled in aluminum hull, and with the mode of laser welding by battery cover board together with case weld.The battery size made is 523450(thickness 5.2mm, width 34mm, length 50mm), nominal capacity 1400mAh.
In the battery through the degassed operation such as to dewater, inject electrolyte, concentration of electrolyte is 1mol/L, and lithium salts is lithium hexafluoro phosphate (LiPF
6), with the mixture of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) for solvent, wherein the ratio of each carbonic ester is DMC: EMC: EC=1: 1: 1, then adds 2%(volume ratio in the electrolytic solution) vinylene carbonate (VC) and 3% vinylethylene carbonate (VEC).
Multistage electricizing activation is adopted according to during initial charge after fluid injection, first with 70mA (0.05C) constant current charge 1 hour, again with 280mA (0.2C) constant current charge to 4.0V, finally charge to 4.2V with 70mA (0.05C) and complete initial charge; Then compressed steel pearl is carried out in a conventional manner and discharge and recharge obtains silicon-based anode lithium ion battery.
Gained silicon-based anode lithium ion battery is at room temperature with 700mA(0.5C) current discharge, initial discharge capacity is 1480mAh, with the capability retention after 0.5C circulation 500 times for 82%.
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., then coated, dry, rolling, cut, obtain positive plate.
Be that the graphite of 6 μm is as lithium ion battery negative pole active materials using average grain diameter, be 91: 5: 2: 2 in mass ratio with Kynoar, Super P conductive carbon, additive scale graphite, be hybridly prepared into graphite cathode slurry with solvent N-methyl pyrilidone etc.Simultaneously, using Si-C composite material as lithium ion battery negative pole active materials, be 88: 7: 2: 3 in mass ratio with Kynoar, Super P conductive carbon, additive scale graphite, be hybridly prepared into silicon-carbon composite cathode slurry with solvent N-methyl pyrilidone etc.
Apply the thick silicon-carbon cathode coating of one deck 50 μm at negative current collector copper foil surface, dry; Then apply the thick graphite cathode coating of one deck 20 μm again at silicon-carbon cathode coating surface, dry; And then apply silicon-carbon cathode coating, graphite cathode coating successively as stated above at the another side of Copper Foil, gained cathode membrane through rolling, cut and obtain composite layered structure negative plate.
Be welded on by aluminium pole ears on positive plate, nickel tab welding, on negative plate, will weld the positive plate of lug, negative plate and the mode of barrier film by reeling, the battery formed, is assembled in aluminum hull, and with the mode of laser welding by battery cover board together with case weld.The battery size made is 523450(thickness 5.2mm, width 34mm, length 50mm), nominal capacity 1400mAh.
In the battery through the degassed operation such as to dewater, inject electrolyte, concentration of electrolyte is 1mol/L, and lithium salts is lithium hexafluoro phosphate (LiPF
6), with the mixture of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) for solvent, wherein the ratio of each carbonic ester is DMC: EMC: EC=1: 1: 1, then adds 1%(volume ratio in the electrolytic solution) vinylene carbonate (VC) and 4% vinylethylene carbonate (VEC).
Multistage electricizing activation is adopted according to during initial charge after fluid injection, first with 70mA (0.05C) constant current charge 1 hour, again with 280mA (0.2C) constant current charge to 4.0V, finally charge to 4.2V with 70mA (0.05C) and complete initial charge; Then compressed steel pearl is carried out in a conventional manner and discharge and recharge obtains silicon-based anode lithium ion battery.
Gained silicon-based anode lithium ion battery is at room temperature with 700mA(0.5C) current discharge, initial discharge capacity is 1415mAh, with the capability retention after 0.5C circulation 500 times for 85%.
Claims (3)
1. manufacture a method for silicon-based anode lithium ion battery, comprise positive plate preparation, prepared by negative plate, assembling, filling electrolyte, and cell activation step, is characterized in that:
Step prepared by described negative plate is: respectively graphite, binding agent and additive are mixed with graphite cathode slurry, and Si-C composite material, binding agent and additive are mixed with silicon-carbon cathode slurry; Apply in the following manner: apply one deck graphite cathode coating at negative current collector copper foil surface, dry; Then apply one deck silicon-carbon cathode coating at graphite cathode coating surface, dry; Then apply one deck graphite cathode coating again at silicon-carbon cathode coating surface, dry; The diaphragm obtained through rolling, cut and obtain the composite layered structure negative plate that coating layer of active substance is graphite/Si-C composite material/graphite;
Described cell activation step employing first and last section is the multistage electricizing activation of small area analysis; Described multistage electricizing activation refers to: during lithium ion battery initial charge, employing first and last section is the multistage electricizing activation of small area analysis, first 0.05C constant current charge 1 hour, then 0.2C constant current charge is to 4.0V, and last 0.05C charges to 4.2V and completes initial charge.
2. the silicon-based anode lithium ion battery obtained in accordance with the method for claim 1, 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 plus plate current-collecting body, negative plate comprises negative current collector and is distributed in the negative electrode active material on negative current collector, it is characterized in that:
Described negative electrode active material is the coating layer of active substance containing Si-C composite material be located on described negative plate, and described coating layer of active substance is the composite layered structure comprising graphite cathode coating and silicon-carbon cathode coating;
Described graphite cathode coating and the composite layered structure of silicon-carbon cathode coating are graphite/Si-C composite material/graphite;
Described graphite cathode coating comprises graphite, binding agent and the additive of average grain diameter 3-6 μm, 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 μm, and described silicon-carbon cathode coating layer thickness is 30-100 μm.
3. silicon-based anode lithium ion battery according to claim 2, it is characterized in that: be except the vinylene carbonate of 1% ~ 3% except adding volume ratio in described electrolyte, also adding vinylethylene carbonate, one or both in methane-disulfonic acid methylene ester that volume ratio is 2% ~ 4%.
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| CN103794817A (en) * | 2014-02-20 | 2014-05-14 | 福建创鑫科技开发有限公司 | Application of vinyl ethylene carbonate to lithium ion battery |
| CN105185995B (en) * | 2015-09-10 | 2018-04-20 | 中天储能科技有限公司 | A kind of silicon/carbon/graphite in lithium ion batteries silicon-carbon composite cathode |
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| CN113921756B (en) * | 2020-07-10 | 2023-05-26 | 兰溪致德新能源材料有限公司 | Silicon-carbon negative electrode piece with high silicon content and preparation method thereof |
| CN112271271B (en) * | 2020-10-15 | 2021-11-23 | 广州汽车集团股份有限公司 | Negative plate, preparation method, lithium ion battery core, lithium ion battery pack and application of lithium ion battery pack |
| CN113078291A (en) * | 2021-03-26 | 2021-07-06 | 珠海冠宇电池股份有限公司 | Negative plate, preparation method thereof and battery |
| CN113488636B (en) * | 2021-06-18 | 2023-04-07 | 江苏正力新能电池技术有限公司 | Composite negative electrode material, negative plate and lithium ion battery |
| CN114284466A (en) * | 2021-12-27 | 2022-04-05 | 珠海冠宇电池股份有限公司 | Negative plate, battery and electronic equipment |
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