CN104701500A - Preparation method of lithium ion battery composite cathode material, cathode material and battery - Google Patents
Preparation method of lithium ion battery composite cathode material, cathode material and battery Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 104
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 99
- 239000010406 cathode material Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 75
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 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 9
- 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
- 239000011135 tin Substances 0.000 claims abstract description 9
- 229910052718 tin Inorganic materials 0.000 claims abstract description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052737 gold Inorganic materials 0.000 claims abstract description 8
- 239000010931 gold Substances 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 35
- 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 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 238000005253 cladding Methods 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052744 lithium Inorganic materials 0.000 abstract description 9
- 230000008602 contraction Effects 0.000 abstract description 3
- 239000002082 metal nanoparticle Substances 0.000 abstract description 3
- 238000007323 disproportionation reaction Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 238000003780 insertion Methods 0.000 abstract 1
- 230000037431 insertion Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000011856 silicon-based particle Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 94
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 56
- 239000010703 silicon Substances 0.000 description 56
- 239000000377 silicon dioxide Substances 0.000 description 47
- 235000012239 silicon dioxide Nutrition 0.000 description 36
- 229910052710 silicon Inorganic materials 0.000 description 31
- 229910052814 silicon oxide Inorganic materials 0.000 description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000012298 atmosphere Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000005543 nano-size silicon particle Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000011056 performance test Methods 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
- 239000004246 zinc acetate Substances 0.000 description 4
- 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
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000000126 substance Substances 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
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011246 composite particle Substances 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
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000009829 pitch coating Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- 239000002345 surface coating layer Substances 0.000 description 2
- YWOHYLAFBNLCLK-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;platinum Chemical compound [Pt].OC(=O)CC(O)(C(O)=O)CC(O)=O YWOHYLAFBNLCLK-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 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
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 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
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- -1 ethyl carbonate ester Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 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
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 preparation method of a lithium ion battery composite cathode material, a cathode material and a battery. The preparation method of the composite cathode material comprises the following steps: 1)performing a disproportionation on silicon monoxide to obtain a first mixture, 2)mixing the first mixture and metal acetate and/or metal citrate and calcining to obtain a lithium ion battery composite cathode material, wherein metal is one or more from copper, nickel, tin, zinc, silver, gold and platinum. A structure of the lithium ion battery composite cathode material is characterized in that metal is coated on the first mixture. Copper, nickel, tin, zinc, silver, gold and platinum have good conductivity, metal nano particles coated on the surface of the first mixture are capable of effectively reducing contact resistance among silicon particles in the lithium ion battery composite cathode material and increasing material conductivity, in the cycle of volume expansion and contraction due to lithium insertion/extraction property of the material, conductivity can be effectively kept, and specific capacity attenuation of the material can be alleviated.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of preparation method of composite cathode material for lithium ion cell, negative material, battery.
Background technology
At present, the lithium ion battery of production and application mainly adopts graphite negative electrodes material, but the embedding lithium capacity of the theory of graphite is 372mAh/g, and reality reaches 370mAh/g, therefore, graphite negative electrodes material on capacity almost without room for promotion.
The nearly more than ten years, various novel high power capacity and high magnification negative material are developed, wherein silica-base material becomes study hotspot due to its high specific discharge capacity (theoretical specific capacity of silicon is 4200mAh/g), but this material in doff lithium process along with serious volumetric expansion and contraction, cause the electroactive material powder of detached on electrode, finally cause capacity attenuation.In order to overcome the special capacity fade of silicon based anode material, generally that silicon and other inactive metals (as Fe, Al, Cu etc.) are formed alloy, as Chinese patent CN03116070.0 discloses silicon aluminium alloy/carbon composite material used for lithium ion battery negative electrode and preparation method thereof; Or homogenize material is distributed in other active or non-active materials and forms composite material (as Si-C, Si-TiN etc.), as Chinese patent CN02112180.X discloses Si-C composite material and the preparation method of used as negative electrode of Li-ion battery height ratio capacity.More conventional method is the Surface coating one deck amorphous carbon at silicon nanoparticle, as CN200910027938.1 discloses the composite negative pole material of a kind of half fluidised form pitch-coating nano-silicon and graphite; CN200910037666.3 discloses a kind of preparation method of composite negative pole material of pitch-coating nano-silicon.
Although alleviate the capacity attenuation of silicon based anode material to a certain extent in the method for nano silica fume Surface coating amorphous carbon, but due to the business-like nano silica fume even micron silica flour that said method adopts, silica flour is difficult to reach nano level in the base and is uniformly dispersed, so fundamentally can not suppress the bulk effect in charge and discharge process, capacity still can be decayed along with the increase of cycle-index quickly.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, a kind of preparation method of composite cathode material for lithium ion cell, negative material, battery are provided, its outer surface of composite cathode material for lithium ion cell is coated with the nano particle of metal, can effectively reduce intergranular contact resistance, increase material conductivity, the volumetric expansion caused at material doff lithium with shrink and circulate, also effectively can maintain conductivity, the special capacity fade of material can be alleviated.
The technical scheme that solution the technology of the present invention problem adopts is to provide a kind of preparation method of composite cathode material for lithium ion cell, comprises the following steps:
(1) obtain the first mixture after silicon monoxide generation disproportionated reaction, this first mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.Find after testing: in the composite material of silicon and silicon dioxide, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale (1nm ~ 50nm), silicon accounts for 25 ~ 33% of the first mixture quality, and silicon dioxide accounts for 50 ~ 67% of the first mixture quality;
(2) calcine after described first mixture being mixed with the acetate of metal and/or the citrate of metal, wherein, described metal is one or more in copper, nickel, tin, zinc, silver, gold, platinum, obtain composite cathode material for lithium ion cell, the structure of this composite cathode material for lithium ion cell is for be coated with described metal at described first mixture.
In the preparation process of above-mentioned composite cathode material for lithium ion cell, during the citrate pyrolysis of the acetate of metal or metal, the reducibility gas such as carbon monoxide and hydrogen can be produced, also carbon can be produced, reducing metal ions all can be become nano-metal particle by these reducibility gas and carbon, there is redox reaction in the acetate of such metal or the citrate of metal self, can form uniform metal carbonyl coat on the surface of the first mixture.
Preferably, the particle diameter of described silicon monoxide is 1000 ~ 15000 orders.
Preferably, the gross mass of the described metal of described first mixture outer cladding accounts for 5 ~ 40% of described composite cathode material for lithium ion cell quality.
Preferably, the gross mass of the described metal of described first mixture outer cladding accounts for 10 ~ 25% of described composite cathode material for lithium ion cell quality.
Preferably, be 5 ~ 100nm at the particle diameter of the described metal of described first mixture outer cladding.
Preferably, described in described step (1), the temperature of silicon monoxide disproportionated reaction is 700 ~ 1200 DEG C, and the time is 0.5 ~ 24 hour.
Preferably, in described step (2) by the concrete grammar that described first mixture mixes with the acetate of metal and/or the citrate of metal be: the citrate of the acetate of described metal and/or described metal is joined in ball grinder, add acetic acid again or ethanol (ratio added is 1:1) does dispersant, add described first mixture again, then ball milling 2 ~ 12 hours.
Preferably, the calcining heat in described step (2) is 250 ~ 550 DEG C, and calcination time is 0.5 ~ 4 hour.
The present invention also provides a kind of lithium ion battery negative material, comprises the composite cathode material for lithium ion cell prepared by above-mentioned preparation method.
Preferably, described lithium ion battery negative material also comprises graphite, and described composite cathode material for lithium ion cell accounts for 5 ~ 30% of the gross mass of the mixture of described composite cathode material for lithium ion cell and described graphite.
The present invention also provides a kind of lithium ion battery, and its negative pole comprises above-mentioned lithium ion battery negative material.
Metal material of copper, nickel, tin, zinc, silver, gold, platinum have good conductivity, at the coated above-mentioned metal nanoparticle of the first mixture outer surface, effectively can reduce the contact resistance between the silicon grain in composite cathode material for lithium ion cell, increase the conductivity of material, in the volumetric expansion caused at material doff lithium and the circulation of contraction, also effectively can maintain conductivity, the special capacity fade of material can be alleviated.The present invention utilizes chemical method at the composite particles Surface coating layer of metal nano particle of nano-silicon and silicon dioxide, utilize the good conductive ability of metal material and stability to increase the conductivity of lithium ion battery composite material, obtain the composite cathode material for lithium ion cell of excellent performance.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with embodiment, the present 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) silicon monoxide powder (particle diameter is 1000 orders) is placed in crucible; and put into atmosphere furnace; 1100 DEG C are warmed up under the protection of argon gas atmosphere; heat 0.5 hour at such a temperature; silicon monoxide generation disproportionated reaction generates the composite material of silicon and silicon dioxide; the mol ratio of silicon and silicon dioxide is 1:1; because silicon monoxide can be reunited after high temperature sintering; so the particle diameter of the first mixture finally obtained is comparatively large, need to make its particle diameter reach 1000 ~ 15000 object scopes through ball milling.This first mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.Find after testing: in the composite material of silicon and silicon dioxide, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale 30nm, and silicon accounts for 20% of the first mixture quality, and silicon dioxide accounts for 40% of the first mixture quality.
(2) zinc acetate is joined in ball grinder, then add dispersant acetic acid (ratio of zinc acetate and acetic acid is 1:1) in ball grinder, then add the first mixture that step (1) obtains, then ball milling 2 hours.Mixture after ball milling is calcined 2 hours at 350 DEG C, obtain composite cathode material for lithium ion cell, the structure of this composite cathode material for lithium ion cell is for be coated with zinc at described first mixture, and zinc accounts for 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 pyrolysis, the reducibility gas such as carbon monoxide and hydrogen can be produced, also carbon can be produced, these reducibility gas and carbon all can restore nano-metal particle, there is redox reaction in such zinc acetate self, can form thick zinc coating layer on the surface of the first mixture.
Gained composite cathode material for lithium ion cell is mixed according to mass ratio 80: 10: 10 with conductive agent acetylene black, binding agent PVDF respectively, use NMP(1-N-methyl-2-2-pyrrolidone N-) this mixture is modulated into slurry, evenly be coated on Copper Foil, 100 DEG C of vacuumize 24 hours, obtained experimental cell pole piece.Be to electrode with lithium sheet, electrolyte is the LiPF6 solution of 1mol/L, solvent is EC(ethyl carbonate ester)+DMC(dimethyl carbonate) (volume ratio 1: 1), barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.
The present embodiment provides a kind of lithium ion battery negative material to comprise composite cathode material for lithium ion cell prepared by above-mentioned preparation method.
The charge-discharge performance test of the button cell that composite cathode material for lithium ion cell prepared by the present embodiment is made: first discharge specific capacity is 858mAh/g, the specific discharge capacity after 100 times that circulates is 523mAh/g.
Metal material zinc has good conductivity, at the nano particle of the coated above-mentioned metallic zinc of the first mixture outer surface, can effectively reduce intergranular contact resistance, increase material conductivity, the volumetric expansion caused at material doff lithium with shrink and circulate, also effectively can maintain conductivity, the special capacity fade of material can be alleviated.The present embodiment utilizes chemical method at the nano particle of the composite particles Surface coating layer of metal zinc of nano-silicon and silicon dioxide, utilize the good conductive ability of metal material and stability to increase the conductivity of lithium ion battery composite material, obtain the composite cathode material for lithium ion cell of excellent performance.
The stabilization ratio capacity of the composite cathode material for lithium ion cell of the present embodiment synthesis is greater than 800mAh/g, nano silicon particles is evenly distributed in silica substrate, nano silicon particles is stoped on the one hand in repeatedly doff lithium process, " electrochemistry sintering " to occur and reunite, on the other hand due to silicon dioxide in doff lithium process without change in volume, so the bulk effect of whole composite cathode material for lithium ion cell also greatly reduces, the conductive network that silicon grain and metal carbonyl coat are formed contacts closely and keeps always, thus 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 process is short, process easily controls, easily realize suitability for industrialized production.
Embodiment 2
The present embodiment provides a kind of preparation method of composite cathode material for lithium ion cell, comprises the following steps:
(1) silicon monoxide powder (particle diameter is 15000 orders) is placed in crucible; and put into atmosphere furnace; 1000 DEG C are warmed up under the protection of argon gas atmosphere; heat 5 hours at such a temperature; silicon monoxide generation disproportionated reaction generates the composite material of silicon and silicon dioxide; the mol ratio of silicon and silicon dioxide is 1:1; because silicon monoxide can be reunited after high temperature sintering; so the particle diameter of the first mixture finally obtained is comparatively large, need to make its particle diameter reach 1000 ~ 15000 object scopes through ball milling.This first mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.Find after testing: in the composite material of silicon and silicon dioxide, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale 10nm, and silicon accounts for 18% of the first mixture quality, and silicon dioxide accounts for 38% of the first mixture quality.
(2) silver citrate is joined in ball grinder, then add in dispersant ethanol to ball grinder and disperse, then add the first mixture that step (1) obtains, then ball milling 4 hours.Mixture after ball milling is calcined 2 hours at 250 DEG C, obtain composite cathode material for lithium ion cell, the structure of this composite cathode material for lithium ion cell is for be coated with silver at described first mixture, and silver accounts for 5% of composite cathode material for lithium ion cell quality, and the particle diameter of silver is 5nm.
The present embodiment provides a kind of lithium ion battery negative material to comprise composite cathode material for lithium ion cell prepared by above-mentioned preparation method.
According to the method preparing button cell in embodiment 1, the obtained lithium ion battery negative material of the present embodiment is used to make button cell, and charge-discharge performance test is carried out to this battery: first discharge specific capacity is 600mAh/g, and the specific discharge capacity after 100 times that circulates is 450mAh/g.
Embodiment 3
The present embodiment provides a kind of preparation method of composite cathode material for lithium ion cell, comprises the following steps:
(1) silicon monoxide powder (particle diameter is 10000 orders) is placed in crucible; and put into atmosphere furnace; 800 DEG C are warmed up under the protection of argon gas atmosphere; heat 12 hours at such a temperature; silicon monoxide generation disproportionated reaction generates the composite material of silicon and silicon dioxide, and this first mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.Find after testing: in the composite material of silicon and silicon dioxide, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale 1nm, and silicon accounts for 10% of the first mixture quality, and silicon dioxide accounts for 21% of the first mixture quality.
(2) nickel acetate is joined in ball grinder, then add in dispersant ethanol to ball grinder and disperse, then add the first mixture that step (1) obtains, then ball milling 4 hours.Mixture after ball milling is calcined 0.5 hour at 550 DEG C, obtain composite cathode material for lithium ion cell, the structure of this composite cathode material for lithium ion cell is for be coated with nickel at described first mixture, and nickel accounts for 40% of composite cathode material for lithium ion cell quality, and the particle diameter of nickel is 40nm.
The present embodiment provides a kind of lithium ion battery negative material to comprise composite cathode material for lithium ion cell prepared by above-mentioned preparation method.
According to the method preparing button cell in embodiment 1, the obtained lithium ion battery negative material of the present embodiment is used to make button cell, and charge-discharge performance test is carried out to this battery: first discharge specific capacity is 831mAh/g, and the specific discharge capacity after 100 times that circulates is 515mAh/g.
Embodiment 4
The present embodiment provides a kind of preparation method of composite cathode material for lithium ion cell, comprises the following steps:
(1) silicon monoxide powder (particle diameter is 8000 orders) is placed in crucible; and put into atmosphere furnace; 700 DEG C are warmed up under the protection of argon gas atmosphere; heat 24 hours at such a temperature; silicon monoxide generation disproportionated reaction generates the composite material of silicon and silicon dioxide, and this first mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.Find after testing: in the composite material of silicon and silicon dioxide, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale 1nm, and silicon accounts for 8% of the first mixture quality, and silicon dioxide accounts for 21% of the first mixture quality.
(2) copper citrate is joined in ball grinder, then add in dispersant acetic acid to ball grinder and disperse, then add the first mixture that step (1) obtains, then ball milling 5 hours.Mixture after ball milling is calcined 2.5 hours at 400 DEG C, obtain composite cathode material for lithium ion cell, the structure of this composite cathode material for lithium ion cell is for be coated with copper at described first mixture, and copper accounts for 25% of composite cathode material for lithium ion cell quality, and the particle diameter of copper is 60nm.
The present embodiment provides a kind of lithium ion battery negative material to comprise composite cathode material for lithium ion cell prepared by above-mentioned preparation method.
According to the method preparing button cell in embodiment 1, the obtained lithium ion battery negative material of the present embodiment is used to make button cell, and charge-discharge performance test is carried out to this battery: first discharge specific capacity is 1387mAh/g, and the specific discharge capacity after 100 times that circulates is 695mAh/g.
Embodiment 5
The present embodiment provides a kind of preparation method of composite cathode material for lithium ion cell, comprises the following steps:
(1) silicon monoxide powder (particle diameter is 6000 orders) is placed in crucible; and put into atmosphere furnace; 900 DEG C are warmed up under the protection of argon gas atmosphere; heat 4 hours at such a temperature; silicon monoxide generation disproportionated reaction generates the composite material of silicon and silicon dioxide, and this first mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.Find after testing: in the composite material of silicon and silicon dioxide, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale 2nm, and silicon accounts for 26% of the first mixture quality, and silicon dioxide accounts for 52% of the first mixture quality.
(2) copper citrate and citric acid tin to be joined in ball grinder (wherein, the mass ratio of copper citrate and citric acid tin is 1:1), add again in dispersant ethanol to ball grinder and disperse, then add the first mixture that step (1) obtains, then ball milling 2 hours.Mixture after ball milling is calcined 4 hours at 400 DEG C, obtain composite cathode material for lithium ion cell, the structure of this composite cathode material for lithium ion cell is for be coated with copper and tin at described first mixture, the gross mass of copper and tin accounts for 30% of composite cathode material for lithium ion cell quality, the particle diameter of copper is 80nm, and the particle diameter of tin is 60nm.
The present embodiment provides a kind of lithium ion battery negative material to comprise composite cathode material for lithium ion cell prepared by above-mentioned preparation method.
According to the method preparing button cell in embodiment 1, the obtained lithium ion battery negative material of the present embodiment is used to make button cell, and charge-discharge performance test is carried out to this battery: first discharge specific capacity is 1027mAh/g, and the specific discharge capacity after 100 times that circulates is 683mAh/g.
Embodiment 6
The present embodiment provides a kind of preparation method of composite cathode material for lithium ion cell, comprises the following steps:
(1) silicon monoxide powder (particle diameter is 4000 orders) is placed in crucible; and put into atmosphere furnace; 1200 DEG C are warmed up under the protection of argon gas atmosphere; heat 18 hours at such a temperature; silicon monoxide generation disproportionated reaction generates the composite material of silicon and silicon dioxide; because silicon monoxide can be reunited after high temperature sintering, so the particle diameter of the first mixture finally obtained is comparatively large, need to make its particle diameter reach 1000 ~ 15000 object scopes through ball milling.This first mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.Find after testing: in the composite material of silicon and silicon dioxide, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale 50nm, and silicon accounts for 30% of the first mixture quality, and silicon dioxide accounts for 63% of the first mixture quality.
(2) acetic acid gold is joined in ball grinder, then add in dispersant acetic acid to ball grinder and disperse, then add the first mixture that step (1) obtains, then ball milling 8 hours.Mixture after ball milling is calcined 3 hours at 300 DEG C, obtain composite cathode material for lithium ion cell, the structure of this composite cathode material for lithium ion cell is for be coated with gold at described first mixture, and gold accounts for 10% of composite cathode material for lithium ion cell quality, and the particle diameter of gold is 100nm.
The present embodiment provides a kind of lithium ion battery negative material to comprise composite cathode material for lithium ion cell prepared by above-mentioned preparation method.
Embodiment 7
The present embodiment provides a kind of preparation method of composite cathode material for lithium ion cell, comprises the following steps:
(1) silicon monoxide powder (particle diameter is 12000 orders) is placed in crucible; and put into atmosphere furnace; 1000 DEG C are warmed up under the protection of argon gas atmosphere; heat 6 hours at such a temperature; silicon monoxide generation disproportionated reaction generates the composite material of silicon and silicon dioxide; because silicon monoxide can be reunited after high temperature sintering, so the particle diameter of the first mixture finally obtained is comparatively large, need to make its particle diameter reach 1000 ~ 15000 object scopes through ball milling.This first mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.Find after testing: in the composite material of silicon and silicon dioxide, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale 20nm, and silicon accounts for 25% of the first mixture quality, and silicon dioxide accounts for 52% of the first mixture quality.
(2) citric acid platinum is joined in ball grinder, then add in dispersant ethanol to ball grinder and disperse, then add the first mixture that step (1) obtains, then ball milling 12 hours.Mixture after ball milling is calcined 1 hour at 450 DEG C, obtain composite cathode material for lithium ion cell, the structure of this composite cathode material for lithium ion cell is for be coated with platinum at described first mixture, and platinum accounts for 15% of composite cathode material for lithium ion cell quality, and the particle diameter of platinum is 50nm.
The present embodiment provides a kind of lithium ion battery negative material to comprise composite cathode material for lithium ion cell prepared by above-mentioned preparation method.
Be understandable that, the illustrative embodiments that above execution mode is only used to principle of the present invention is described and adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (10)
1. a preparation method for composite cathode material for lithium ion cell, is characterized in that, comprises the following steps:
(1) the first mixture is obtained after silicon monoxide generation disproportionated reaction;
(2) calcine after described first mixture being mixed with the acetate of metal and/or the citrate of metal, wherein, described metal is one or more in copper, nickel, tin, zinc, silver, gold, platinum, obtain composite cathode material for lithium ion cell, the structure of this composite cathode material for lithium ion cell is for be coated with described metal at described first mixture.
2. the preparation method of composite cathode material for lithium ion cell according to claim 1, is characterized in that, the particle diameter of described silicon monoxide is 1000 ~ 15000 orders.
3. the preparation method of composite cathode material for lithium ion cell according to claim 1, is characterized in that, the gross mass of the described metal of described first mixture outer cladding accounts for 5 ~ 40% of described composite cathode material for lithium ion cell quality.
4. the preparation method of composite cathode material for lithium ion cell according to claim 3, is characterized in that, is 5 ~ 100nm at the particle diameter of the described metal of described first mixture outer cladding.
5. the preparation method of composite cathode material for lithium ion cell according to claim 1, is characterized in that, described in described step (1), the temperature of silicon monoxide disproportionated reaction 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 characterized in that, in described step (2) by the concrete grammar that described first mixture mixes with the acetate of metal and/or the citrate of metal be: the citrate of the acetate of described metal and/or described metal is joined in ball grinder, add acetic acid again or ethanol does dispersant, add described first mixture again, then ball milling 2 ~ 12 hours.
7. the preparation method of composite cathode material for lithium ion cell according to claim 1, is characterized in that, the calcining heat in described step (2) is 250 ~ 550 DEG C, and calcination time is 0.5 ~ 4 hour.
8. a lithium ion battery negative material, is characterized in that, comprises the composite cathode material for lithium ion cell prepared by the preparation method described in claim 1 ~ 7.
9. lithium ion battery negative material according to claim 8, is characterized in that, also comprises graphite, and described composite cathode material for lithium ion cell accounts for 5 ~ 30% of the gross mass of the mixture of described composite cathode material for lithium ion cell and described graphite.
10. a lithium ion battery, is characterized in that, its negative pole comprises the lithium ion battery negative material described in claim 8 or 9.
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