CN101777651B - Silicon anode material and preparation method thereof and lithium battery using silicon anode material - Google Patents
Silicon anode material and preparation method thereof and lithium battery using silicon anode material Download PDFInfo
- Publication number
- CN101777651B CN101777651B CN200910104890XA CN200910104890A CN101777651B CN 101777651 B CN101777651 B CN 101777651B CN 200910104890X A CN200910104890X A CN 200910104890XA CN 200910104890 A CN200910104890 A CN 200910104890A CN 101777651 B CN101777651 B CN 101777651B
- Authority
- CN
- China
- Prior art keywords
- silicon dioxide
- reducing agent
- preparation
- carbonaceous reducing
- negative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 28
- 239000010703 silicon Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 14
- 239000010405 anode material Substances 0.000 title abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 30
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 29
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 50
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims description 23
- 239000011149 active material Substances 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 14
- 230000004888 barrier function Effects 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
- 238000005554 pickling Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000000571 coke Substances 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000013543 active substance Substances 0.000 abstract 3
- 239000006172 buffering agent Substances 0.000 abstract 3
- 238000000034 method Methods 0.000 description 17
- 230000008569 process Effects 0.000 description 12
- 239000006258 conductive agent Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- -1 hexafluoroarsenate lithium Chemical compound 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000713 high-energy ball milling Methods 0.000 description 3
- 159000000002 lithium salts Chemical group 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910010586 LiFeO 2 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NOJZFGZMTUAHLD-UHFFFAOYSA-N [Li].[Cl] Chemical compound [Li].[Cl] NOJZFGZMTUAHLD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000012071 phase 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
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides an anode material of a lithium battery, which comprises an active substance and a volume buffering agent. The active substance is coated or partly coated on the surfaces of the particles of the volume buffering agent. The active substance is silicon. The volume buffering agent is silicon dioxide. The invention also provides a preparation method for the anode material, wherein silicon dioxide of powder and powder of a carbon reducing agent which are subjected to pretreatment are subjected to vacuum high temperature sintering; and based on the total weight of the silicon dioxide and the carbon reducing agent, the weight of the carbon reducing agent occupies 16.67 to 35.8 percent of the total weight. The anode material provided by the invention has good cycle performance and high capacity.
Description
Technical field
The invention belongs to the lithium ion battery field.The lithium battery that the present invention is specifically related to a kind of silicon-based anode material and preparation method thereof and uses this material.
Background technology
But lithium ion battery receives widely with a series of significant advantages such as its operating voltage is high, specific energy is big, in light weight, volume is little, have extended cycle life, memory-less effect fast charging and discharging and non-environmental-pollution and paying close attention to.Along with the continuous development of lithium ion battery, people also have higher requirement to the performance of lithium ion battery.In this case, research and development have more that the lithium ion battery material of height ratio capacity better cycle ability has very important strategic importance.
Silica-base material is the most promising negative material that can satisfy lithium ion battery requirement of new generation at present.Silicon materials are compared with material with carbon element, and the specific capacity of silicon is high, and its theoretical capacity is up to 4200mAh/g.
But because silicon is in charging and discharging process, violent variation can take place in volume, can destroy the structure of material, causes the cyclical stability of electrode unstable, thereby causes battery failure.And its first irreversible capacity is high, has limited its application as lithium ion battery negative material.
Therefore present many researchs all are devoted to improve and optimize on the performance of silicon-based anode material.
The compound system that the silicon grain outerwrap amorphous carbon layer of employing chemical gaseous phase deposition (CVD) method preparation is arranged at present; The structure and the electric conductivity of silicon materials have been improved; Can restrain the lithium embedding to a certain extent and deviate from the bulk effect in the process, thereby the cycle performance of said material is improved.But the process of CVD method is difficult to control, and uncertain factor is many, therefore is difficult to realize producing in batches.
Summary of the invention
Technical problem to be solved by this invention is: not can manufacture the good silicium cathode material of cycle performance in the prior art.
The silicon composite that is used for the lithium ion battery negative pole that the present invention provides stable cycle performance to produce in batches.
A kind of negative material of lithium ion battery comprises active material and volume buffer, and said active material coats or partly be coated on the surface of the particle of volume buffer, and said active material is a silicon, and said volume buffer is a silicon dioxide.
The present invention also provides a kind of preparation method of above-mentioned negative material, and it comprises: will pass through the powder of pretreated silicon dioxide and the powder vacuum high-temperature sintering of carbonaceous reducing agent; Total weight with silicon dioxide and carbonaceous reducing agent is a benchmark, and the weight of carbonaceous reducing agent accounts for 16.67%-35.8%.
The 3rd purpose of the present invention provides a kind of lithium ion battery; It comprises: battery case, pole piece and electrolyte; Said pole piece and electrolyte sealing are contained in the battery case, and said pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and said positive pole comprises collector and loads on the positive electrode on the collector; Said negative pole comprises collector and loads on the negative material on the collector that said negative material is a negative material provided by the present invention.
Inventor of the present invention finds unexpectedly,, coats or the part coated silica with silicon as coating layer with active material silicon, can effectively suppress volumetric expansion, increases cycle performance.Inventor of the present invention thinks, coats silicon at silica surface, because silicon is coating layer; And coating thickness is less; So lithium ion can embed in the active material silicon easily, and at the surperficial negative material that coats other materials of pure silicon, lithium ion reacts with the surface of its particle easily; And the reacting phase of granule interior causes specific capacity low to difficulty.The inventor infers: because the present invention makes with the particle reduction; Silicon in most of negative material is not the surface that is coated on silicon dioxide fully; But in the zonal coating of silica surface, form discontinuous coating band, longitudinal dilatation and lateral expansion in the time of the silicon change in volume can effectively being suppressed like this; Thereby the powder of detached of effectively avoiding the silicon volumetric expansion to bring, the cycle performance of raising battery.
Negative material powder of detached problem provided by the present invention is obviously improved, thereby has effectively improved the cycle performance of battery.And the specific capacity of negative material provided by the present invention is higher relatively.
Description of drawings
Fig. 1 is the sem photograph (2000 times) of the negative material A1 of the embodiment of the invention 1.
Fig. 2 is the XRD figure of the negative material A1 of the embodiment of the invention 1.
Embodiment
A kind of negative material of lithium ion battery comprises active material and volume buffer, and said active material coats or partly be coated on the surface of the particle of volume buffer, and said active material is a silicon, and said volume buffer is a silicon dioxide.
The average grain diameter of said negative material is 5-20 μ m.
The coating thickness of said active material is 1-8 μ m.
The mass ratio of said active material and said volume buffer is 1: 3-4: 1.So both height ratio capacity can be kept, good cycle can be kept again.
A kind of preparation method of above-mentioned negative material, it comprises: will pass through the powder of pretreated silicon dioxide and the powder vacuum high-temperature sintering of carbonaceous reducing agent; Total weight with silicon dioxide and carbonaceous reducing agent is a benchmark, and the weight of carbonaceous reducing agent accounts for 16.67%-35.8%.
The preparation raw material of said silicon dioxide is meant that natural purity reaches the quartz sand more than 99%, wherein possibly contain Al
3O
2, CaO, Fe
2O
3And P
2O
5Deng impurity.
Said preliminary treatment is meant that it is the superfine silicon dioxide of 5-20 μ m that the silicon dioxide powder breakdown mill is become particle diameter, then superfine silicon dioxide is carried out chemical pickling drying again.
Said pulverizing is ground and is mechanical high-energy ball milling under protection gas atmosphere, and wherein said protection gas is inert gas.
Said chemical pickling can be known in those skilled in the art, and also can be preferably following mode chemical pickling: earlier the superfine silicon dioxide powder is put into chloroazotic acid and stir 3h, to remove heavy metal, metal ion/compound washes with pure water then repeatedly; Superfine silicon dioxide powder after will washing is again put into mass percentage concentration 0.96wt% hydrofluoric acid solution and is stirred 3h, to remove the dephosphorization boride.Wash repeatedly with pure water then, remove chemistry acid.
Said chemical pickling can also comprise that the SiO 2 powder with the process chemical pickling utilizes centrifuge dewatering, and oven drying makes its water content＜1%.
The material of said carbonaceous reducing agent is preferably one or more in coke, native graphite, Delanium and the carbonaceous mesophase spherules; Coke more preferably.
The powder of said carbonaceous reducing agent is meant the above-mentioned material with average grain diameter＜50 μ m, and crushing and classification, shaping and purification process prepare the powder that average grain diameter is 0.1-1 μ m.
Said crushing and classification, shaping and purification process etc. are operating as known in those skilled in the art.
During high temperature sintering, the average grain diameter of said silicon dioxide and said carbonaceous reducing agent ratio is preferably 10: 1-100: 1.
Said high temperature sintering is meant that in sintering furnace following reaction: SiO takes place for silicon dioxide and carbonaceous reducing agent under 1000-2000 ℃ the vacuum environment
2+ 2C=Si+2CO ↑.
Heating rate is preferably 1-10 ℃/min.
The time of said high temperature sintering is preferably 1-24h.
Said sintering furnace is conventionally known to one of skill in the art, for example can be various resistance furnace, induction furnace, arc furnace, crucible etc.The preferred corundum crucible of the present invention.
The present invention is through the ratio of carbonaceous reducing agent and silicon dioxide in the control raw material, controls the ratio of silicon in the negative material of generation.Silicon dioxide is excessive among the present invention, and carbonaceous reducing agent is a silicon with the silicon dioxide partial reduction only, and the relative silica dioxide granule of carbonaceous reducing agent particle is less, mixes to guarantee that carbonaceous reducing agent reacts completely and the covered effect of the silicon that produces is better.Method provided by the invention can be used for industrial mass manufacture fully, and preparation technology is simple relatively.
A kind of lithium ion battery; It comprises: battery case, pole piece and electrolyte; Said pole piece and electrolyte sealing are contained in the battery case, and said pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and said positive pole comprises collector and loads on positive electrode and the conductive agent on the collector; Said negative pole comprises collector and loads on negative material and the conductive agent on the collector that said negative material is a negative material provided by the present invention.
In lithium ion battery of the present invention, electrolyte can be nonaqueous electrolytic solution.Said nonaqueous electrolytic solution is the solution that electrolyte lithium salt forms in nonaqueous solvents, can use the nonaqueous electrolytic solution of routine well known by persons skilled in the art.Can be selected from lithium hexafluoro phosphate (LiPF like electrolyte lithium salt
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), hexafluorosilicic acid lithium (LiSiF
6), tetraphenyl lithium borate (LiB (C
6H
5)
4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl
4) and fluorocarbon based sulfonic acid lithium (LiC (SO
2CF
3)
3), LiCH
3SO
3, LiN (SO
2CF
3)
2In one or more.Nonaqueous solvents can be selected from chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be fluorine-containing for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain in the chain organosilane ester of unsaturated bond one or more.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain in the ring-type organosilane ester of unsaturated bond one or more for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton.In said nonaqueous electrolytic solution, the concentration of electrolyte lithium salt is generally the 0.1-2 mol, is preferably the 0.8-1.2 mol.
In lithium rechargeable battery of the present invention, barrier film is arranged between positive pole and the negative pole, has electrical insulation capability and liquid retainability ability.Said barrier film can be selected from and well known to a person skilled in the art various barrier films used in the lithium rechargeable battery, for example polyolefin micro porous polyolefin membrane (PP), polyethylene felt (PE), glass mat or ultra-fine fibre glass paper or PP/PE/PP.Said barrier film also can be a polyimide film.Said polyimide film can be polyimide film known in those skilled in the art, and preferably its porosity is 20%-55%, and average pore diameter is the 30-120 nanometer.
In lithium rechargeable battery of the present invention, positive electrode active materials can adopt the positive electrode active materials of various routines, like LiFePO4, Li
3V
2(PO
4)
3, LiMn
2O
4, LiMnO
2, LiNiO
2, LiCoO
2, LiVPO
4F and LiFeO
2In one or more.In order significantly to improve said positive electrode active materials performance, said positive electrode active materials is preferably LiFePO4, LiCoO
2, LiVPO
4Among the F one or more.
Wherein, said conductive agent is known in those skilled in the art, and conductive agent generally comprises one or more in graphite powder, carbon black, CNT, HV, titanium valve and the copper powder.
Total weight with negative material and conductive agent is a benchmark, and the weight percentage of said conductive agent is 5-30%.
The preparation method of lithium rechargeable battery provided by the invention carries out according to method as well known to those skilled in the art, and in general, this method comprises anodal, negative pole and the barrier film between positive pole and the negative pole formation pole piece of reeling successively; Pole piece is inserted in the battery case, add electrolyte, then sealing; Wherein, Said negative pole comprises collector and loads on the negative active core-shell material on the collector that wherein, said negative active core-shell material is a negative active core-shell material provided by the invention.Wherein, the method for coiling and sealing is that those skilled in the art are known.The consumption of electrolyte is a conventional amount used.
Through concrete embodiment the present invention is done further explanation below.
Embodiment 1
With the quartz sand of purity more than 99%, mechanical high-energy ball milling to 10 μ m makes the superfine silicon dioxide powder in argon gas atmosphere.
Again the superfine silicon dioxide powder is put into chloroazotic acid and stir 3h, filter the back and wash repeatedly with pure water; Put into mass percentage concentration 0.96wt% hydrofluoric acid again and stir 3h, filter the back and wash repeatedly with pure water; Put into centrifuge then and dewater,, make its water content＜1% at 100 ℃ of oven drying 5h.Process through pretreated SiO 2 powder.
With coke blacking mechanical high-energy ball milling in argon gas atmosphere of average grain diameter＜50 μ m, broken classification prepares the carbonaceous reducing agent that granularity is 0.5 μ m.
360 grams are mixed through pretreated SiO 2 powder and 120 gram carbonaceous reducing agents, fully stir 12h, make it to mix.Send into then under 1000 ℃ the vacuum environment and react, insulation 3h drops to room temperature then, promptly makes negative material A1.
From the sem photograph of Fig. 1, the particle diameter that can find out A1 is roughly about 10 μ m.
From the XRD figure of Fig. 2, can find out: through contrasting with standard diagram, Si can be confirmed to contain at the peak of 28.36,47.23,56.04,69.04,76.32 degree in 2 θ angles; SiO can be confirmed to contain at the peak of 11.92,18.91,21.74,23.35,24.22,50.79 degree in 2 θ angles
2
Embodiment 2
Different is that 420 grams are mixed through pretreated SiO 2 powders and 120 gram carbonaceous reducing agents with embodiment 1.Make negative material A2.
Embodiment 3
Different is that 360 grams are mixed through pretreated SiO 2 powders and 80 gram carbonaceous reducing agents with embodiment 1.Make negative material A3.
Embodiment 4
Different is with embodiment 1, and the average grain diameter of said silicon dioxide is 10 μ m, and the average grain diameter of said carbonaceous reducing agent is 0.1 μ m.Make negative material A4.
Embodiment 5
Different is with embodiment 1, and the average grain diameter of said silicon dioxide is 10 μ m, and the average grain diameter of said carbonaceous reducing agent is 1 μ m.Make negative material A5.
Embodiment 6
(1) preparation of positive pole
With 8.8Kg N-methyl pyrrolidone (NMP), 1Kg acetylene black and 0.2Kg polyvinylidene fluoride (PVDF) powder, stir and be mixed with the acetylene black wash in 5 minutes.
Get the above-mentioned acetylene black slurry for preparing of 2Kg, add 3KgN-methyl pyrrolidone (NMP), 10Kg cobalt acid lithium (the auspicious auspicious company in Hunan produces particle diameter 8 μ m), 0.3Kg polyvinylidene fluoride (PVDF), stir and promptly get battery anode active material after 20 minutes.
Above-mentioned anode active material of lithium ion battery is coated on the aluminum foil current collector that thickness is 20 μ m, and after drying, roll-in and the cut-parts, making length is that 400mm, width are that 44mm, thickness are the positive plate of 0.15mm.
(2) preparation of negative pole
100Kg negative material A1,10kg conductive agent carbon black, 3Kg adhesive butadiene-styrene latex (SBR), 3Kg carboxymethyl cellulose (CMC) are joined in the 50Kg water, in mixer, stir then and form cathode size stable, homogeneous.This slurry is coated on the Copper Foil that thickness is 20 μ m equably, through 120 ℃ of oven dry, roll-in and cut-parts, is that 410mm, width are that 45mm, thickness are the negative plate of 0.18mm thereby make length.
(3) assembling of battery
The positive plate that (1) is obtained, negative plate and the PP/PE/PP barrier film that (2) obtain stack gradually the electrode group that is wound into scroll; The electrode group that obtains is put into the battery case of an end opening; (solvent is an ethylene carbonate: diethyl carbonate=1: 1 (volume ratio) to inject electrolyte 3 grams; LiPF6 concentration be 1 rub/liter), process lithium ion battery F1 after the sealing No. 053450.
Embodiment 7
Different is that negative material is A2, processes lithium ion battery F2 with embodiment 4.
Embodiment 8
Different is that negative material is A3, processes lithium ion battery F3 with embodiment 4.
Embodiment 9
Different is that negative material is A4, processes lithium ion battery F4 with embodiment 4.
Different is that negative material is A5, processes lithium ion battery F5 with embodiment 4.
Comparative Examples 1
Different is that negative material is a pure silicon, processes lithium ion battery H1 with embodiment 4.Performance test
The specific capacity test:
With thickness is that 0.06 millimeter, diameter are that 16 millimeters, weight are that the metal lithium sheet of 0.0064 gram is a negative electrode active material, with the modified polypropene barrier film, with the LiPF of 1 mol
6Solution is electrolyte, and the A1-A5 and pure silicon, conductive carbon black and the Kynoar that are made by the foregoing description 1-5 and Comparative Examples 1 with 0.125 gram are positive electrode with 70: 10: 20 mixture of weight ratio, process button cell S1-S5 and J1.
Battery S1-S5 shelved change into to 0.2 volt of voltage with 0.2 milliampere of electric current after 60 minutes; Then respectively with 1 milliampere, 0.9 milliampere, 0.8 milliampere, 0.7 milliampere, 0.6 milliampere constant current discharge to 0.005 volt; After shelving 30 minutes; Again with 0.5 milliampere, 0.4 milliampere, 0.3 milliampere, 0.2 milliampere, 0.1 milliampere, 0.09 milliampere, 0.08 milliampere, 0.07 milliampere, 0.06 milliampere, 0.05 milliampere constant current discharge to 0.005 volt; Shelve after 30 minutes with 0.5 milliampere of electric current constant current charge; Record charges to cell voltage and reaches 2.5 volts time; According to normal capacity (MAH)=charging current (milliampere) * charging interval of battery (hour) normal capacity of counting cell, normal capacity promptly gets the electrochemical specific capacity of GND active material (A1-A5 and J1) divided by the weight of the negative active core-shell material (A1-A5 and J1) of battery, the result is as shown in table 1.
The cycle performance test:
Under the room temperature, with battery (F1-F5 and H1) with 1C electric current constant current charge to 4.2V, lower voltage limit 2V, cut-off current 0.02C; And then with battery with 1C electric current constant-current discharge to 3.V.Repeat above step 150 time, obtain the capacity of 150 circulation backs of battery normal temperature 1C current discharge, battery capacity conservation rate after the computation cycles to 3.0V.The result sees table 2.
Table 1
| Negative material | A1 | A2 | A3 | A4 | A5 | Silicon |
| Specific capacity (mAh/g) | 2052 | 1698 | 1326 | 2104 | 1985 | 2997 |
Table 2
| Battery | F1 | F2 | F3 | F4 | F5 | H1 |
| 150 circulation volume conservation rates (%) | 71.2 | 81.7 | ?89.6 | 74.7 | ?69.1 | 0 |
Annotate: H1 capability retention after circulation 35 times is 0.
Can find out from table 1 and table 2,,, still keep higher specific capacity in art technology people acceptable scope though specific capacity of the present invention is lower than the specific capacity of pure silicon.But 150 circulation volume conservation rates of battery of the present invention can reach about 70%, have well solved the problem of the cycle performance difference of silica-base material.
Claims (9)
1. the negative material of a lithium ion battery comprises active material and volume buffer, and said active material coats or partly be coated on the surface of the particle of volume buffer, and said active material is a silicon, and said volume buffer is a silicon dioxide; The average grain diameter of said negative material is 5-20 μ m; The coating thickness of said active material is 1-8 μ m; The mass ratio of said active material and said volume buffer is 1: 3-4: 1.
2. the preparation method of the described negative material of claim 1, it comprises: will pass through the powder of pretreated silicon dioxide and the powder vacuum high-temperature sintering of carbonaceous reducing agent; Total weight with silicon dioxide and carbonaceous reducing agent is a benchmark, and the weight of carbonaceous reducing agent accounts for 16.67%-35.8%.
3. preparation method according to claim 2 is characterized in that: said preliminary treatment is meant that it is the superfine silicon dioxide of 5-20 μ m that the silicon dioxide powder breakdown mill is become average grain diameter, carries out chemical pickling with superfine silicon dioxide then.
4. preparation method according to claim 2 is characterized in that: said carbonaceous reducing agent comprises one or more in coke, native graphite, Delanium and the carbonaceous mesophase spherules.
5. preparation method according to claim 4 is characterized in that: said carbonaceous reducing agent is a coke.
6. preparation method according to claim 2 is characterized in that: the average grain diameter of said carbonaceous reducing agent is 0.1-1 μ m.
7. preparation method according to claim 2 is characterized in that: the average grain diameter ratio of said silicon dioxide and said carbonaceous reducing agent is 10: 1-100: 1.
8. preparation method according to claim 2 is characterized in that: the temperature of said high temperature sintering is 1000-2000 ℃, and heating rate is 1-10 ℃/min, and the high temperature sintering time is 1-24h.
9. lithium rechargeable battery; It comprises: battery case, pole piece and electrolyte; Said pole piece and electrolyte sealing are contained in the battery case, and said pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and said positive pole comprises collector and loads on the positive electrode on the collector; Said negative pole comprises collector and loads on the negative material on the collector that said negative material is the described negative material of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910104890XA CN101777651B (en) | 2009-01-12 | 2009-01-12 | Silicon anode material and preparation method thereof and lithium battery using silicon anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910104890XA CN101777651B (en) | 2009-01-12 | 2009-01-12 | Silicon anode material and preparation method thereof and lithium battery using silicon anode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101777651A CN101777651A (en) | 2010-07-14 |
| CN101777651B true CN101777651B (en) | 2012-06-20 |
Family
ID=42514040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910104890XA Active CN101777651B (en) | 2009-01-12 | 2009-01-12 | Silicon anode material and preparation method thereof and lithium battery using silicon anode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101777651B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5621867B2 (en) * | 2012-03-27 | 2014-11-12 | Tdk株式会社 | Lithium ion secondary battery |
| CN102820451A (en) * | 2012-07-23 | 2012-12-12 | 深圳市海太阳实业有限公司 | Negative electrode pole piece and preparation method thereof, and lithium ion battery and preparation method thereof |
| JP5967024B2 (en) * | 2013-06-20 | 2016-08-10 | 信越化学工業株式会社 | Non-aqueous electrolyte secondary battery active material, negative electrode molded body, and non-aqueous electrolyte secondary battery |
| CN105406050B (en) * | 2015-12-31 | 2018-11-02 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of comprehensive silicon negative material, preparation method and purposes |
| CN106328909B (en) * | 2016-11-18 | 2020-01-24 | 深圳市贝特瑞新能源材料股份有限公司 | Nano silicon dioxide-silicon-based composite material, preparation method and lithium ion battery containing composite material |
| JP6941302B2 (en) * | 2017-01-11 | 2021-09-29 | Jnc株式会社 | Polysilsesquioxane-coated silicon nanoparticles or their fired product and its manufacturing method, negative electrode active material for lithium ion batteries, negative electrode for lithium ion batteries, and lithium ion batteries |
| JP6969483B2 (en) * | 2018-04-09 | 2021-11-24 | トヨタ自動車株式会社 | Lithium-ion secondary battery and its manufacturing method |
| CN110364662B (en) * | 2018-04-11 | 2022-07-05 | 宁德新能源科技有限公司 | Separators and Electrochemical Devices |
| CN113176300A (en) * | 2021-04-25 | 2021-07-27 | 南方科技大学 | Photoelectric humidity sensor based on artificial opal humidity-sensitive material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1428880A (en) * | 2001-12-26 | 2003-07-09 | 信越化学工业株式会社 | Conductive silicon oxide powder, its mfg. method and negative electrode material of nonaqueous electrolyte secodary battery |
| KR20040082803A (en) * | 2003-03-20 | 2004-09-30 | 삼성에스디아이 주식회사 | Negative active material for lithium secondary battery and method of preparing same |
| JP2006216374A (en) * | 2005-02-03 | 2006-08-17 | Sony Corp | Negative electrode material and battery using it |
| CN1895999A (en) * | 2006-06-08 | 2007-01-17 | 复旦大学 | Silicon/oxidative silicon nuclear-shell structured nano-composite material, its preparation and use |
-
2009
- 2009-01-12 CN CN200910104890XA patent/CN101777651B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1428880A (en) * | 2001-12-26 | 2003-07-09 | 信越化学工业株式会社 | Conductive silicon oxide powder, its mfg. method and negative electrode material of nonaqueous electrolyte secodary battery |
| KR20040082803A (en) * | 2003-03-20 | 2004-09-30 | 삼성에스디아이 주식회사 | Negative active material for lithium secondary battery and method of preparing same |
| JP2006216374A (en) * | 2005-02-03 | 2006-08-17 | Sony Corp | Negative electrode material and battery using it |
| CN1895999A (en) * | 2006-06-08 | 2007-01-17 | 复旦大学 | Silicon/oxidative silicon nuclear-shell structured nano-composite material, its preparation and use |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2006216374A 2006.08.17 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101777651A (en) | 2010-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101777651B (en) | Silicon anode material and preparation method thereof and lithium battery using silicon anode material | |
| KR101494715B1 (en) | Negative active material for rechargeable lithium battery, method of preparing the same, and negative electrode and rechargeable lithium battery including the same | |
| CN101047246B (en) | Positive electrode active material for secondary battery and secondary battery | |
| KR20220092556A (en) | Anode active material for battery and manufacturing method thereof, battery negative electrode, battery | |
| TWI482346B (en) | Method of manufacturing cathode material for lithium secondary battery | |
| EP2626931A1 (en) | Negative active material for rechargeable lithium battery and rechargeable lithium battery including same | |
| CN116022771B (en) | Hard carbon material, negative electrode plate and electrochemical device | |
| CN113488637B (en) | Composite negative electrode material, negative plate and lithium ion battery | |
| CN112490518B (en) | Positive electrode lithium supplement additive, preparation method thereof, positive electrode and lithium ion battery | |
| CN101740766B (en) | Cathode active material, preparation method thereof and lithium battery using same | |
| CN109309207B (en) | Positive electrode active material, preparation method thereof, positive electrode and lithium ion battery | |
| CN111342031B (en) | Multi-element gradient composite high-first-efficiency lithium battery negative electrode material and preparation method thereof | |
| CN114057198A (en) | Lithium-doped silicon-based oxide negative electrode active material, preparation method thereof, and negative electrode and secondary battery including the same | |
| EP2672553B1 (en) | Nonaqueous electrolyte secondary battery | |
| CN107565099B (en) | Positive active material, preparation method thereof and lithium ion battery | |
| KR101796248B1 (en) | Cathode active material for lithium secondary battery and method of preparing the same | |
| KR20150021406A (en) | Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| CN103693632A (en) | Preparation method of lithium vanadyl phosphate positive material for lithium ion battery | |
| CN112510180A (en) | Silicon oxide-carbon filament active material and preparation method and application thereof | |
| CN101752544B (en) | Silicon cathode and preparation method thereof and Li-ion secondary battery comprising silicon cathode | |
| CN101937993B (en) | Anode material and preparation method thereof and battery | |
| JP2003100292A (en) | Carbon material for negative electrode and manufacturing method thereof, and lithium ion secondary battery using the same | |
| CN115893400B (en) | Preparation method of negative electrode material for long-cycle lithium ion battery | |
| JP2009280466A (en) | Manufacturing apparatus for electrochemical active material, manufacturing method of electrochemical active material, and non-aqueous electrolyte secondary battery | |
| WO2019024221A1 (en) | Preparation method for high-first-efficiency long-life silicon-carbon cathode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |