CN104701500B - A kind of preparation method of composite cathode material for lithium ion cell, negative material, battery - Google Patents
A kind of preparation method of composite cathode material for lithium ion cell, negative material, battery Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 101
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 96
- 239000000463 material Substances 0.000 title claims abstract description 60
- 239000010406 cathode material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 73
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims abstract description 9
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- 239000011135 tin Substances 0.000 claims abstract description 9
- 229910052718 tin Inorganic materials 0.000 claims abstract description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052737 gold Inorganic materials 0.000 claims abstract description 7
- 239000010931 gold Substances 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 239000004332 silver Substances 0.000 claims abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 33
- 238000000498 ball milling Methods 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005253 cladding Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000002923 metal particle Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 59
- 229910052710 silicon Inorganic materials 0.000 abstract description 59
- 239000010703 silicon Substances 0.000 abstract description 59
- 229910052744 lithium Inorganic materials 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000002082 metal nanoparticle Substances 0.000 abstract description 3
- -1 wherein Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 94
- 239000000377 silicon dioxide Substances 0.000 description 47
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000012298 atmosphere Substances 0.000 description 15
- 239000000758 substrate Substances 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000010792 warming Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000005543 nano-size silicon particle Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000004246 zinc acetate Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- IOVSQAQVXZOFTD-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;tin Chemical compound [Sn].OC(=O)CC(O)(C(O)=O)CC(O)=O IOVSQAQVXZOFTD-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000012946 outsourcing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- CHUYYOSIZBKMJD-UHFFFAOYSA-N acetic acid;gold Chemical compound [Au].CC(O)=O CHUYYOSIZBKMJD-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 238000009829 pitch coating Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 229940071575 silver citrate Drugs 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- QUTYHQJYVDNJJA-UHFFFAOYSA-K trisilver;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ag+].[Ag+].[Ag+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QUTYHQJYVDNJJA-UHFFFAOYSA-K 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation method of composite cathode material for lithium ion cell, negative material, battery, the preparation method of the composite negative pole material comprises the following steps：（1）Silicon monoxide obtains the first mixture after disproportionated reaction occurs；（2）Calcined after first mixture is mixed with the acetate of metal and/or the citrate of metal, wherein, metal is the one or more in copper, nickel, tin, zinc, silver, gold, platinum, composite cathode material for lithium ion cell is obtained, the structure of the composite cathode material for lithium ion cell is to be coated with metal in the first mixture.Copper, nickel, tin, zinc, silver, gold, platinum have good electric conductivity, above-mentioned metal nanoparticle is coated in the first mixing exterior surface, the contact resistance that can be effectively reduced between the silicon grain in composite cathode material for lithium ion cell, increase the electric conductivity of material, in volumetric expansion caused by the embedding de- lithium of material and the circulation shunk, electric conductivity can be effectively maintained, the special capacity fade of material can be alleviated.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of preparation of composite cathode material for lithium ion cell
Method, negative material, battery.
Background technology
At present, the lithium ion battery of production and application mainly uses graphite negative electrodes material, but the theoretical embedding lithium capacity of graphite
For 372mAh/g, actual to have reached 370mAh/g, therefore, graphite negative electrodes material is on capacity almost without room for promotion.
Nearly more than ten years, various new high power capacity and high magnification negative material are developed, wherein silica-base material due to
Its high specific discharge capacity（The theoretical specific capacity of silicon is 4200mAh/g）And turn into study hotspot, but this material is embedding de-
Along with serious volumetric expansion and contraction during lithium, cause the electroactive material powder of detached on electrode, ultimately result in appearance
Amount decay.In order to overcome the special capacity fade of silicon based anode material, usually by silicon and other inactive metals（As Fe, Al,
Cu etc.）Alloy is formed, as Chinese patent CN03116070.0 discloses silicon aluminium alloy/carbon composite material used for lithium ion battery negative electrode
And preparation method thereof；Or material is evenly spread in other activity or non-active material and forms composite（Such as Si-C, Si-
TiN etc.）, as Chinese patent CN02112180.X discloses the Si-C composite material and system of used as negative electrode of Li-ion battery height ratio capacity
Preparation Method.More conventional method, is one layer of amorphous carbon of Surface coating in silicon nanoparticle, such as CN200910027938.1
A kind of composite negative pole material of half fluidised form pitch-coating nano-silicon and graphite is disclosed；CN200910037666.3 discloses a kind of drip
The preparation method of the composite negative pole material of green grass or young crops cladding nano-silicon.
Although silicon based anode material is alleviated to a certain extent in the method for nano silica fume Surface coating amorphous carbon
Capacity attenuation, but due to the commercialized nano silica fume even micron silica flour that the above method uses, silica flour is difficult to reach in the base
It is uniformly dispersed to nano level, so can not fundamentally suppress the bulk effect in charge and discharge process, capacity still can be with
The increase of cycle-index and decay quickly.
The content of the invention
The technical problems to be solved by the invention are for above shortcomings in the prior art, there is provided a kind of lithium ion
The preparation method of battery composite cathode material, negative material, battery, its outer surface of composite cathode material for lithium ion cell are coated with
The nano particle of metal, intergranular contact resistance can be effectively reduced, increase material conductivity, caused by the embedding de- lithium of material
Volumetric expansion also can effectively maintain electric conductivity, can alleviate the special capacity fade of material with shrinking in circulation.
Technical scheme is to provide a kind of composite cathode material for lithium ion cell used by solving present invention problem
Preparation method, comprise the following steps：
（1）Silicon monoxide obtains the first mixture after disproportionated reaction occurs, and first mixture includes part unreacted
Silicon monoxide and the composite of silicon and silica.Find after testing：In the composite of silicon and silica, silicon
It is distributed in silica substrate, and the particle diameter of the silicon is nanoscale (1nm~50nm), silicon accounts for the 25 of the first mixture quality
~33%, silica accounts for the 50~67% of the first mixture quality；
（2）Calcined after first mixture is mixed with the acetate of metal and/or the citrate of metal, wherein,
The metal is the one or more in copper, nickel, tin, zinc, silver, gold, platinum, obtains composite cathode material for lithium ion cell, the lithium
The structure of ion battery composite negative pole material is to be coated with the metal in first mixture.
In the preparation process of above-mentioned composite cathode material for lithium ion cell, the acetate of metal or the citrate of metal
During pyrolytic, the reducibility gas such as carbon monoxide and hydrogen can be produced, can also produce carbon, these reducibility gas and carbon all can
Metal ion is reduced into nano-metal particle, oxidation occurs for the acetate of such metal or the citrate of metal itself also
Original reaction, can form uniform metal carbonyl coat on the surface of the first mixture.
Preferably, the particle diameter of the silicon monoxide is 1000~15000 mesh.
Preferably, the gross mass of the metal of the first mixture outer cladding accounts for the lithium ion battery Compound Negative
The 5~40% of pole quality of materials.
Preferably, the gross mass of the metal of the first mixture outer cladding accounts for the lithium ion battery Compound Negative
The 10~25% of pole quality of materials.
Preferably, it is 5~100nm in the particle diameter of the metal of the first mixture outer cladding.
Preferably, the step（1）Described in the temperature of silicon monoxide disproportionated reaction be 700~1200 DEG C, the time is
0.5~24 hour.
Preferably, the step（2）It is middle by first mixture and the acetate of metal and/or the citric acid of metal
Salt mixing specific method be：The citrate of the acetate of the metal and/or the metal is added in ball grinder, then
(ratio of addition is 1 for addition acetic acid or ethanol:1) dispersant is done, adds first mixture, then ball milling 2~12 is small
When.
Preferably, the step（2）In calcining heat be 250~550 DEG C, calcination time be 0.5~4 hour.
The present invention also provides a kind of lithium ion battery negative material, including as the lithium ion prepared by above-mentioned preparation method
Battery composite cathode material.
Preferably, described lithium ion battery negative material also includes graphite, the lithium ion battery composite cathode material
Material accounts for the 5~30% of the composite cathode material for lithium ion cell and the gross mass of the mixture of the graphite.
The present invention also provides a kind of lithium ion battery, and its negative pole includes above-mentioned lithium ion battery negative material.
Metal material of copper, nickel, tin, zinc, silver, gold, platinum have good electric conductivity, in the first mixing exterior surface cladding
Metal nanoparticle is stated, the contact resistance that can be effectively reduced between the silicon grain in composite cathode material for lithium ion cell, increase
The electric conductivity of material, can in volumetric expansion caused by the embedding de- lithium of material with the circulation of contraction, also can effectively maintain electric conductivity
To alleviate the special capacity fade of material.The present invention is using chemical method in nano-silicon and the composite particles Surface coating one of silica
Layer metal nanoparticle, increases leading for lithium ion battery composite material using the good conductive ability and stability of metal material
Electrically, the composite cathode material for lithium ion cell of excellent performance is obtained.
Embodiment
To make those skilled in the art more fully understand technical scheme, with reference to embodiment to this
Invention is described in further detail.
Embodiment 1
The present embodiment provides a kind of preparation method of composite cathode material for lithium ion cell, comprises the following steps：
（1）By silicon monoxide powder（Particle diameter is 1000 mesh）It is placed in crucible, and is put into atmosphere furnace, in argon gas atmosphere
1100 DEG C are warming up under protection, is heated 0.5 hour at such a temperature, disproportionated reaction generation silicon and silica occur for silicon monoxide
Composite, the mol ratio of silicon and silica is 1:1, because silicon monoxide can reunite after high temperature sintering, institute
It is larger, it is necessary to make its particle diameter reach the scopes of 1000~15000 mesh by ball milling with the particle diameter of the first mixture finally given.
First mixture includes the unreacted silicon monoxide in part and the composite of silicon and silica.Find after testing：
In the composite of silicon and silica, silicon is distributed in silica substrate, and the particle diameter of the silicon is nanoscale 30nm,
Silicon accounts for the 20% of the first mixture quality, and silica accounts for the 40% of the first mixture quality.
（2）Zinc acetate is added in ball grinder, adding dispersant acetic acid, (ratio of zinc acetate and acetic acid is 1:1) arrive
In ball grinder, step is added（1）The first obtained mixture, then ball milling 2 hours.By the mixture after ball milling at 350 DEG C
Lower calcining 2 hours, obtains composite cathode material for lithium ion cell, and the structure of the composite cathode material for lithium ion cell is described
First mixture is coated with zinc, and zinc accounts for the 20% of composite cathode material for lithium ion cell quality, and the particle diameter of zinc is 20nm.
In the preparation process of above-mentioned composite cathode material for lithium ion cell, during zinc acetate pyrolytic, an oxidation can be produced
The reducibility gas such as carbon and hydrogen, can also produce carbon, and these reducibility gas and carbon can all restore nano-metal particle, so
Redox reaction occurs for zinc acetate itself, and the zinc clad of thickness can be formed on the surface of the first mixture.
By gained composite cathode material for lithium ion cell respectively with conductive agent acetylene black, binding agent PVDF according to mass ratio 80
: 10: 10 mixing, use NMP（1-Methyl-2-Pyrrolidone）This mixture is modulated into slurry, is coated uniformly on copper foil, 100
DEG C vacuum drying 24 hours, obtained experimental cell pole piece.Using lithium piece as to electrode, electrolyte is 1mol/L LiPF6 solution,
Solvent is EC（Ethyl carbonate ester）+DMC（Dimethyl carbonate）（Volume ratio 1: 1）, barrier film is celgard2400 films, full of
CR2025 type button cells are assembled into the glove box of argon gas atmosphere.
The present embodiment, which provides a kind of lithium ion battery negative material, includes the lithium-ion electric prepared by above-mentioned preparation method
Pond composite negative pole material.
The charge-discharge performance for the button cell that composite cathode material for lithium ion cell manufactured in the present embodiment is made is surveyed
Examination：First discharge specific capacity is 858mAh/g, and specific discharge capacity is 523mAh/g after circulating 100 times.
Metal material zinc has good electric conductivity, and the nanometer of above-mentioned metallic zinc is coated in the first mixing exterior surface
Grain, intergranular contact resistance can be effectively reduced, increase material conductivity, the volumetric expansion caused by the embedding de- lithium of material is with receiving
In contracting circulation, electric conductivity also can be effectively maintained, the special capacity fade of material can be alleviated.The present embodiment is being received using chemical method
The nano particle of the composite particles Surface coating layer of metal zinc of rice silicon and silica, utilizes the good conductive energy of metal material
Power and stability increase the electric conductivity of lithium ion battery composite material, obtain the lithium ion battery composite cathode of excellent performance
Material.
The stable specific capacity of the composite cathode material for lithium ion cell of the present embodiment synthesis is more than 800mAh/g, silicon nanometer
Grain is evenly distributed in silica substrate, on the one hand prevents nano silicon particles that " electrification occurs during repeatedly embedding de- lithium
Learn sintering " and reunite, on the other hand due to silica during embedding de- lithium without Volume Changes, so whole lithium ion battery
The bulk effect of composite negative pole material also greatly reduces so that silicon grain contacts closely with the conductive network that metal carbonyl coat is formed
And it is always maintained at, so as to effectively slow down the speed of capacity attenuation.
Raw material in the present embodiment is cheap and easy to get, preparation technology is simple, flow is short, process is easily controlled, easily realizes work
Industry metaplasia is produced.
Embodiment 2
The present embodiment provides a kind of preparation method of composite cathode material for lithium ion cell, comprises the following steps：
（1）By silicon monoxide powder（Particle diameter is 15000 mesh）It is placed in crucible, and is put into atmosphere furnace, in argon gas atmosphere
Protection under be warming up to 1000 DEG C, heat 5 hours at such a temperature, disproportionated reaction generation silicon and silica occurs for silicon monoxide
Composite, the mol ratio of silicon and silica is 1:1, because silicon monoxide can reunite after high temperature sintering, institute
It is larger, it is necessary to make its particle diameter reach the scopes of 1000~15000 mesh by ball milling with the particle diameter of the first mixture finally given.
First mixture includes the unreacted silicon monoxide in part and the composite of silicon and silica.Find after testing：
In the composite of silicon and silica, silicon is distributed in silica substrate, and the particle diameter of the silicon is nanoscale 10nm,
Silicon accounts for the 18% of the first mixture quality, and silica accounts for the 38% of the first mixture quality.
（2）Silver citrate is added in ball grinder, dispersant ethanol is added and is disperseed into ball grinder, added
Step（1）The first obtained mixture, then ball milling 4 hours.Mixture after ball milling is calcined 2 hours at 250 DEG C, obtained
Composite cathode material for lithium ion cell, the structure of the composite cathode material for lithium ion cell is in the first mixture outer cladding
There is silver, silver accounts for the 5% of composite cathode material for lithium ion cell quality, and silver-colored particle diameter is 5nm.
The present embodiment, which provides a kind of lithium ion battery negative material, includes the lithium-ion electric prepared by above-mentioned preparation method
Pond composite negative pole material.
According to the method that button cell is prepared in embodiment 1, lithium ion battery negative material made from the present embodiment is used
Button cell is made, and charge-discharge performance test is carried out to the battery：First discharge specific capacity is 600mAh/g, circulation
Specific discharge capacity is 450mAh/g after 100 times.
Embodiment 3
The present embodiment provides a kind of preparation method of composite cathode material for lithium ion cell, comprises the following steps：
（1）By silicon monoxide powder（Particle diameter is 10000 mesh）It is placed in crucible, and is put into atmosphere furnace, in argon gas atmosphere
Protection under be warming up to 800 DEG C, heat 12 hours at such a temperature, disproportionated reaction generation silicon and silica occurs for silicon monoxide
Composite, first mixture includes the unreacted silicon monoxide in part and the composite of silicon and silica.
Find after testing：In the composite of silicon and silica, silicon is distributed in silica substrate, and the particle diameter of the silicon is
Nanoscale 1nm, silicon account for the 10% of the first mixture quality, and silica accounts for the 21% of the first mixture quality.
（2）Nickel acetate is added in ball grinder, dispersant ethanol is added and is disperseed into ball grinder, add step
Suddenly（1）The first obtained mixture, then ball milling 4 hours.Mixture after ball milling is calcined 0.5 hour at 550 DEG C, obtained
Composite cathode material for lithium ion cell, the structure of the composite cathode material for lithium ion cell is in the first mixture outer cladding
There is nickel, nickel accounts for the 40% of composite cathode material for lithium ion cell quality, and the particle diameter of nickel is 40nm.
The present embodiment, which provides a kind of lithium ion battery negative material, includes the lithium-ion electric prepared by above-mentioned preparation method
Pond composite negative pole material.
According to the method that button cell is prepared in embodiment 1, lithium ion battery negative material made from the present embodiment is used
Button cell is made, and charge-discharge performance test is carried out to the battery：First discharge specific capacity is 831mAh/g, circulation
Specific discharge capacity is 515mAh/g after 100 times.
Embodiment 4
The present embodiment provides a kind of preparation method of composite cathode material for lithium ion cell, comprises the following steps：
（1）By silicon monoxide powder（Particle diameter is 8000 mesh）It is placed in crucible, and is put into atmosphere furnace, in argon gas atmosphere
700 DEG C are warming up under protection, is heated 24 hours at such a temperature, disproportionated reaction generation silicon and silica occur for silicon monoxide
Composite, first mixture include the unreacted silicon monoxide in part and the composite of silicon and silica.Through
Detection is found：In the composite of silicon and silica, silicon is distributed in silica substrate, and the particle diameter of the silicon is to receive
Meter level 1nm, silicon account for the 8% of the first mixture quality, and silica accounts for the 21% of the first mixture quality.
（2）Copper citrate is added in ball grinder, dispersant acetic acid is added and is disperseed into ball grinder, added
Step（1）The first obtained mixture, then ball milling 5 hours.Mixture after ball milling is calcined 2.5 hours at 400 DEG C, obtained
To composite cathode material for lithium ion cell, the structure of the composite cathode material for lithium ion cell is in the first mixture outsourcing
Copper is covered with, copper accounts for the 25% of composite cathode material for lithium ion cell quality, and the particle diameter of copper is 60nm.
The present embodiment, which provides a kind of lithium ion battery negative material, includes the lithium-ion electric prepared by above-mentioned preparation method
Pond composite negative pole material.
According to the method that button cell is prepared in embodiment 1, lithium ion battery negative material made from the present embodiment is used
Button cell is made, and charge-discharge performance test is carried out to the battery：First discharge specific capacity is 1387mAh/g, circulation
Specific discharge capacity is 695mAh/g after 100 times.
Embodiment 5
The present embodiment provides a kind of preparation method of composite cathode material for lithium ion cell, comprises the following steps：
（1）By silicon monoxide powder（Particle diameter is 6000 mesh）It is placed in crucible, and is put into atmosphere furnace, in argon gas atmosphere
900 DEG C are warming up under protection, is heated 4 hours at such a temperature, disproportionated reaction generation silicon and silica occur for silicon monoxide
Composite, first mixture include the unreacted silicon monoxide in part and the composite of silicon and silica.Through
Detection is found：In the composite of silicon and silica, silicon is distributed in silica substrate, and the particle diameter of the silicon is to receive
Meter level 2nm, silicon account for the 26% of the first mixture quality, and silica accounts for the 52% of the first mixture quality.
（2）Copper citrate and citric acid tin are added in ball grinder（Wherein, the mass ratio of copper citrate and citric acid tin
For 1:1）, add dispersant ethanol and disperseed into ball grinder, add step（1）The first obtained mixture, then
Ball milling 2 hours.Mixture after ball milling is calcined 4 hours at 400 DEG C, obtains composite cathode material for lithium ion cell, the lithium
The structure of ion battery composite negative pole material is to be coated with copper and tin in first mixture, and the gross mass of copper and tin accounts for lithium
The 30% of ion battery composite negative pole material quality, the particle diameter of copper is 80nm, and the particle diameter of tin is 60nm.
The present embodiment, which provides a kind of lithium ion battery negative material, includes the lithium-ion electric prepared by above-mentioned preparation method
Pond composite negative pole material.
According to the method that button cell is prepared in embodiment 1, lithium ion battery negative material made from the present embodiment is used
Button cell is made, and charge-discharge performance test is carried out to the battery：First discharge specific capacity is 1027mAh/g, circulation
Specific discharge capacity is 683mAh/g after 100 times.
Embodiment 6
The present embodiment provides a kind of preparation method of composite cathode material for lithium ion cell, comprises the following steps：
（1）By silicon monoxide powder（Particle diameter is 4000 mesh）It is placed in crucible, and is put into atmosphere furnace, in argon gas atmosphere
1200 DEG C are warming up under protection, is heated 18 hours at such a temperature, disproportionated reaction generation silicon and silica occur for silicon monoxide
Composite, because silicon monoxide can reunite after high temperature sintering, so the grain of the first mixture finally given
Footpath is larger, it is necessary to make its particle diameter reach the scopes of 1000~15000 mesh by ball milling.It is not anti-that first mixture includes part
The silicon monoxide and silicon and the composite of silica answered.Find after testing：In the composite of silicon and silica,
Silicon is distributed in silica substrate, and the particle diameter of the silicon is nanoscale 50nm, and silicon accounts for the 30% of the first mixture quality,
Silica accounts for the 63% of the first mixture quality.
（2）Acetic acid gold is added in ball grinder, dispersant acetic acid is added and is disperseed into ball grinder, add step
Suddenly（1）The first obtained mixture, then ball milling 8 hours.Mixture after ball milling is calcined 3 hours at 300 DEG C, obtains lithium
Ion battery composite negative pole material, the structure of the composite cathode material for lithium ion cell are to be coated with first mixture
Gold, gold account for the 10% of composite cathode material for lithium ion cell quality, and golden particle diameter is 100nm.
The present embodiment, which provides a kind of lithium ion battery negative material, includes the lithium-ion electric prepared by above-mentioned preparation method
Pond composite negative pole material.
Embodiment 7
The present embodiment provides a kind of preparation method of composite cathode material for lithium ion cell, comprises the following steps：
（1）By silicon monoxide powder（Particle diameter is 12000 mesh）It is placed in crucible, and is put into atmosphere furnace, in argon gas atmosphere
Protection under be warming up to 1000 DEG C, heat 6 hours at such a temperature, disproportionated reaction generation silicon and silica occurs for silicon monoxide
Composite, because silicon monoxide can reunite after high temperature sintering, so the grain of the first mixture finally given
Footpath is larger, it is necessary to make its particle diameter reach the scopes of 1000~15000 mesh by ball milling.It is not anti-that first mixture includes part
The silicon monoxide and silicon and the composite of silica answered.Find after testing：In the composite of silicon and silica,
Silicon is distributed in silica substrate, and the particle diameter of the silicon is nanoscale 20nm, and silicon accounts for the 25% of the first mixture quality,
Silica accounts for the 52% of the first mixture quality.
（2）Citric acid platinum is added in ball grinder, dispersant ethanol is added and is disperseed into ball grinder, added
Step（1）The first obtained mixture, then ball milling 12 hours.Mixture after ball milling is calcined 1 hour at 450 DEG C, obtained
To composite cathode material for lithium ion cell, the structure of the composite cathode material for lithium ion cell is in the first mixture outsourcing
Platinum is covered with, platinum accounts for the 15% of composite cathode material for lithium ion cell quality, and the particle diameter of platinum is 50nm.
The present embodiment, which provides a kind of lithium ion battery negative material, includes the lithium-ion electric prepared by above-mentioned preparation method
Pond composite negative pole material.
It is understood that the principle that embodiment of above is intended to be merely illustrative of the present and the exemplary implementation that uses
Mode, but the invention is not limited in this.For those skilled in the art, the essence of the present invention is not being departed from
In the case of refreshing and essence, various changes and modifications can be made therein, and these variations and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of composite cathode material for lithium ion cell, it is characterised in that comprise the following steps：
(1) silicon monoxide obtains the first mixture after disproportionated reaction occurs；
(2) calcined after first mixture is mixed with the acetate of metal and/or the citrate of metal, calcining heat is
250~550 DEG C, wherein, the metal is the one or more in copper, nickel, tin, zinc, silver, gold, platinum, obtains lithium ion battery and answers
Negative material is closed, the structure of the composite cathode material for lithium ion cell is to be coated with the metal in first mixture,
During the citrate pyrolytic of the acetate of metal or metal, carbon monoxide and hydrogen reduction gas can be produced, can also
Carbon is produced, metal ion can be all reduced into nano-metal particle by these reducibility gas and carbon.
2. the preparation method of composite cathode material for lithium ion cell according to claim 1 a, it is characterised in that oxygen
The particle diameter of SiClx is 1000~15000 mesh.
3. the preparation method of composite cathode material for lithium ion cell according to claim 1, it is characterised in that described first
The gross mass of the metal of mixture outer cladding accounts for the 5~40% of the composite cathode material for lithium ion cell quality.
4. the preparation method of composite cathode material for lithium ion cell according to claim 3, it is characterised in that described
The particle diameter of the metal of one mixture outer cladding is 5~100nm.
5. the preparation method of composite cathode material for lithium ion cell according to claim 1, it is characterised in that the step
(1) temperature of silicon monoxide disproportionated reaction described in is 700~1200 DEG C, and the time is 0.5~24 hour.
6. the preparation method of composite cathode material for lithium ion cell according to claim 1, it is characterised in that the step
(2) it is with the specific method that the acetate of metal and/or the citrate of metal mix by first mixture in：By described in
The citrate of the acetate of metal and/or the metal is added in ball grinder, adds acetic acid or ethanol does dispersant, then
First mixture is added, then ball milling 2~12 hours.
7. the preparation method of composite cathode material for lithium ion cell according to claim 1, it is characterised in that the step
(2) calcination time in is 0.5~4 hour.
8. a kind of lithium ion battery negative material, it is characterised in that including made as the preparation method described in claim 1~7
Standby composite cathode material for lithium ion cell.
9. lithium ion battery negative material according to claim 8, it is characterised in that also including graphite, the lithium ion
Battery composite cathode material account for the gross mass of the mixture of the composite cathode material for lithium ion cell and the graphite 5~
30%.
10. a kind of lithium ion battery, it is characterised in that its negative pole includes the negative electrode of lithium ion battery material described in claim 8 or 9
Material.
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| CN109301222A (en) * | 2018-10-12 | 2019-02-01 | 台州学院 | A kind of NiO/Pt nanometer combined electrode material and preparation method thereof |
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| CN102569726A (en) * | 2010-12-30 | 2012-07-11 | 中国电子科技集团公司第十八研究所 | Method for preparing lithium ion battery anode material coated with metal ions |
| CN103247789A (en) * | 2012-02-13 | 2013-08-14 | 三星Sdi株式会社 | Negative active material, method of preparing the same and rechargeable lithium battery including the same |
| CN103259001A (en) * | 2013-05-06 | 2013-08-21 | 奇瑞汽车股份有限公司 | Silica composite material as well as preparation method thereof and lithium ion battery |
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| CN102569726A (en) * | 2010-12-30 | 2012-07-11 | 中国电子科技集团公司第十八研究所 | Method for preparing lithium ion battery anode material coated with metal ions |
| CN103247789A (en) * | 2012-02-13 | 2013-08-14 | 三星Sdi株式会社 | Negative active material, method of preparing the same and rechargeable lithium battery including the same |
| CN103259001A (en) * | 2013-05-06 | 2013-08-21 | 奇瑞汽车股份有限公司 | Silica composite material as well as preparation method thereof and lithium ion battery |
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