CN104701514A - Lithium ion battery anode material, preparation method thereof and lithium ion battery - Google Patents
Lithium ion battery anode material, preparation method thereof and lithium ion battery Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 98
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000010405 anode material Substances 0.000 title abstract description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 106
- 239000000203 mixture Substances 0.000 claims abstract description 95
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000010703 silicon Substances 0.000 claims abstract description 54
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 38
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims description 80
- 239000002245 particle Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 239000008139 complexing agent Substances 0.000 claims description 26
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 7
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims description 6
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical group [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 50
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 31
- 229910052744 lithium Inorganic materials 0.000 abstract description 31
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 238000007323 disproportionation reaction Methods 0.000 abstract 2
- 230000002687 intercalation Effects 0.000 abstract 2
- 238000009830 intercalation Methods 0.000 abstract 2
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 239000011856 silicon-based particle Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 31
- 238000000498 ball milling Methods 0.000 description 30
- 235000012239 silicon dioxide Nutrition 0.000 description 27
- 229910052814 silicon oxide Inorganic materials 0.000 description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000010406 cathode material Substances 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000011049 pearl Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000010439 graphite Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 239000012456 homogeneous solution Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 235000011150 stannous chloride Nutrition 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003376 silicon Chemical class 0.000 description 3
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009829 pitch coating Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 244000050510 Cunninghamia lanceolata Species 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 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
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- -1 ethyl carbonate ester Chemical class 0.000 description 1
- 101150016402 fsn-1 gene Proteins 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
- 238000002156 mixing Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium ion battery anode material and a preparation method thereof, and a lithium ion battery. A structure of the anode material is characterized in that the mixture obtained by disproportionation of silicon monoxide is plated with tin, silicon in the mixture is distributed in a silica matrix, and silicon particle size is nano-sized. According to the invention, tin is plated, a tin layer plated outside the mixture is a compact layer without a gap. Tin is active metal and has lithium intercalation specific capacity, when the anode material is performed with lithium intercalation, the lithium ions can pass through the tin layer and are intercalated into a core of the anode material, and the core is the mixture obtained by disproportionation of silicon monoxide. Metal tin has good conductivity and stability, in the anode material, the mixture is tightly contacted with a conductive network formed by the tin layer, capacity attenuation speed of the mixture is reduced, and the electrochemistry performance of the anode material is increased.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of lithium ion battery cathode material and its preparation method, lithium ion 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 said method has done certain modification for silicium cathode material, above-mentioned silicium cathode material electrochemical performance is still undesirable.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, a kind of lithium ion battery cathode material and its preparation method, lithium ion battery are provided, the conductive network that the mixture obtained after silicon monoxide disproportionated reaction in this lithium ion battery negative material is formed with its outer tin coating contacts closely, the capacity attenuation speed of the mixture obtained after reducing the silicon monoxide disproportionated reaction as kernel, thus improve the chemical property of lithium ion battery negative material.
The technical scheme that solution the technology of the present invention problem adopts is to provide a kind of lithium ion battery negative material, its structure is be coated with tin outside the mixture that obtains after silicon monoxide disproportionated reaction, in described mixture, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale.
Preferably, the particle diameter of described silicon monoxide is 100 ~ 800 orders, and the particle diameter of described silicon is 1 ~ 50nm.
Preferably, described tin accounts for the mass percent of described lithium ion battery negative material is 1 ~ 30%.
It is further preferred that the mass percent that described tin accounts for described lithium ion battery negative material is 5 ~ 15%.
Preferably, described mixture comprises: the silicon accounting for described mixture quality about 1/3rd, accounts for the silicon dioxide of described mixture quality about 2/3rds.
The present invention also provides a kind of preparation method of above-mentioned lithium ion battery negative material, comprises the following steps:
(1) silicon monoxide generation disproportionated reaction, obtains mixture;
(2) outer zinc-plated at described mixture, obtain lithium ion battery negative material.
Preferably, step is also comprised (i) between described step (1) and described step (2): step (1) described mixture is worn into the particle that particle diameter is 0.1 ~ 10 micron.
Preferably, described in described step (1), the temperature of silicon monoxide disproportionated reaction is 700 ~ 1200 DEG C, and the time of described disproportionated reaction is 0.5 ~ 24 hour.
Preferably, described step (2) at the outer zinc-plated concrete grammar of described mixture is: join the solution containing complexing agent containing Sn
2+acid solution in obtain mixed solution, the more described mixture that this mixed solution and described step (1) obtain is mixed to get suspension, at 50 ~ 90 DEG C, heats 0.5 ~ 4 hour, then add can by described Sn
2+the reducing agent of reduction.
Preferably, the pH value of described acid solution is 2 ~ 6.
Preferably, described containing Sn
2+acid solution in Sn
2+mass percent concentration be 1 ~ 30wt%.
It is further preferred that described containing Sn
2+acid solution in Sn
2+mass percent concentration be 5 ~ 20wt%.
Preferably, complexing agent described in described mixed solution and described Sn
2+mass ratio be (8:1) ~ (25:1).
Preferably, described complexing agent is one or more in thiocarbamide, citric acid, tartaric acid;
Described reducing agent is sodium phosphite and/or hydroquinones.
Preferably, the amount of the described mixture that the described step (1) in suspension described in described step (2) obtains is 5 ~ 30g/ml.
The present invention also provides a kind of lithium ion battery, and its negative pole comprises above-mentioned lithium ion battery negative material.
The structure of the lithium ion battery negative material in the present invention is be coated with tin outside the mixture that obtains after silicon monoxide disproportionated reaction, the mixture obtained after silicon monoxide disproportionated reaction mainly comprises the composite material of silicon and silicon dioxide, and the composite material of this silicon and silicon dioxide is the basis material of lithium ion battery negative material.Tin is coated with outside the mixture obtained after silicon monoxide disproportionated reaction, because tin plates, so the tin coating outside the mixture obtained after silicon monoxide disproportionated reaction is the layer not having space of one deck densification, but this tin coating does not only affect the embedding lithium specific capacity of whole lithium ion battery negative material, but also contribute to the embedding lithium specific capacity improving whole lithium ion battery negative material.This is because tin is active metal, himself there is embedding lithium specific capacity, so when whole ion cathode material lithium carries out embedding lithium, lithium ion can be embedded into the kernel of ion cathode material lithium through tin coating, this kernel is the mixture obtained after silicon monoxide disproportionated reaction.And in ion cathode material lithium, the conductive network that the mixture obtained after silicon monoxide disproportionated reaction is formed with its outer tin coating contacts closely, thus the capacity attenuation speed of the mixture obtained after reducing the silicon monoxide disproportionated reaction as kernel.
Metallic tin has good conductivity and stability, and tin itself has higher embedding lithium specific capacity (theoretical embedding lithium specific capacity is 990mAh/g).So the outer plating tin of the mixture obtained after silicon monoxide disproportionated reaction, can increase the conductivity of lithium ion battery negative material on the one hand; On the other hand, the embedding lithium capacity of tin itself can be utilized to store a part of lithium, increase the embedding lithium specific capacity of composite material.Because the diffusion velocity of lithium ion in metallic tin matrix is very fast, therefore, the diffusion admittance of lithium ion after zinc-plated, can not be stopped, and then improve the chemical property of lithium ion battery negative material on the whole.
The raw material that in the present invention, the preparation method of lithium ion battery negative material uses is easy to get, technique is simple and effectively can suppress the bulk effect of silicon.
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 lithium ion battery negative material, comprises the following steps:
(1) silicon monoxide powder (particle diameter is 300 orders) is placed in crucible; and put into atmosphere furnace; 1200 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; because silicon monoxide can be reunited after high temperature sintering, so the particle diameter of the mixture finally obtained is comparatively large, this mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.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.
(2) mixture is added in ball grinder, then add 4 times of ball milling pearls to the weight of mixture (large and small ball milling pearl adds according to 1:1 ratio).Ball grinder is placed on planetary ball mill, by mixture ball milling 12 hours under the rotating speed of 300 revs/min, is become by this mixture ball milling particle diameter to be the particle of 0.1 micron.
(3) two hydrated stannous chlorides are dissolved in hydrochloric acid, stir and be made into a homogeneous solution in, should containing Sn
2+the pH value of acid solution be 2, wherein, Sn
2+mass percent concentration be 15wt%.
By the solution be configured to containing complexing agent soluble in water for complexing agent thiocarbamide.
Solution containing complexing agent thiocarbamide is added drop-wise to above-mentioned containing Sn
2+acid solution in obtain mixed solution, this mixed solution complexing agent thiocarbamide and Sn
2+mass ratio be 10: 1.This mixed solution is joined in the particle of the mixture that ball milling that step (2) obtains is crossed, ultrasonic disperse obtains suspension in 10 minutes, the amount of the mixture that the ball milling that in this suspension, step (2) obtains is crossed is 10g/ml, then adds reducing agent sodium phosphite, at 50 DEG C, heat 4 hours, do not stop to stir, filter, water washing, drying, obtains lithium ion battery negative material.The structure of this lithium ion battery negative material is be coated with tin outside the mixture that obtains after silicon monoxide disproportionated reaction.Wherein, the quality of tin accounts for the mass percent of lithium ion battery negative material is 5%.
By the preparation method in the present embodiment, the mixture obtained after silicon monoxide disproportionated reaction is outer zinc-plated, can obtain the coating of one deck even compact, thus make ion cathode material lithium have good consistency on the whole.
Gained lithium ion battery negative material 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 LiPF of 1mol/L
6solution, 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 charge-discharge performance test of the button cell that lithium ion battery negative material prepared by the present embodiment is made: first discharge specific capacity is 1358mAh/g, the specific discharge capacity after 100 times that circulates is 651mAh/g.
The structure of the lithium ion battery negative material in the present embodiment is be coated with tin outside the mixture that obtains after silicon monoxide disproportionated reaction, mixture mainly comprises the composite material of silicon and silicon dioxide, and the composite material of this silicon and silicon dioxide is the basis material of lithium ion battery negative material.The composite material of this silicon and silicon dioxide is generated through high temperature disproportionated reaction by silicon monoxide, and silicon is wherein nano-silicon.In the composite material of silicon and silicon dioxide, silicon accounts for the quality of about 1/3rd, and silicon dioxide accounts for the quality of about 2/3rds.In the composite material of silicon and silicon dioxide, in silica, in doff lithium process, the silicon dioxide in the composite material of silicon and silicon dioxide can stop silicon grain in repeatedly doff lithium process, electrochemistry sintering occur and reunite in silicon distribution; And silicon dioxide makes to form the volumetric expansion that good skeletal support well can cushion silicon between silicon grain and silicon grain, reduces the cubical expansivity of whole silica composite material, effectively reduces the capacity attenuation speed of silica composite material.
Lithium ion battery negative material in the present invention, its structure is be coated with tin outside the mixture that obtains after silicon monoxide disproportionated reaction.Tin is coated with outside the mixture obtained after silicon monoxide disproportionated reaction, because tin plates, so the tin coating outside the mixing obtained after silicon monoxide disproportionated reaction is the layer not having space of one deck densification, but this tin coating does not only affect the embedding lithium specific capacity of whole lithium ion battery negative material, but also contribute to the embedding lithium specific capacity improving whole lithium ion battery negative material.This is because tin is active metal, himself there is embedding lithium specific capacity, so when whole ion cathode material lithium carries out embedding lithium, lithium ion can be embedded into the kernel of ion cathode material lithium through tin coating, the mixture obtained after this kernel silicon monoxide disproportionated reaction.
Metallic tin has good conductivity and stability, and tin itself has higher embedding lithium specific capacity (theoretical embedding lithium specific capacity is 990mAh/g).So the outer plating tin of the mixture obtained after silicon monoxide disproportionated reaction, can increase the conductivity of lithium ion battery negative material on the one hand; On the other hand, the embedding lithium capacity of tin itself can be utilized to store a part of lithium, increase the embedding lithium specific capacity of composite material.Because the diffusion velocity of lithium ion in metallic tin matrix is very fast, therefore, the diffusion admittance of lithium ion after zinc-plated, can not be stopped, and then improve the chemical property of lithium ion battery negative material on the whole.
The raw material that in the present invention, the preparation method of lithium ion battery negative material uses is easy to get, technique is simple and effectively can suppress the bulk effect of silicon.
The present embodiment provides a kind of lithium ion battery, and its negative pole comprises above-mentioned lithium ion battery negative material.
Embodiment 2
The present embodiment provides a kind of preparation method of lithium ion battery negative material, comprises the following steps:
(1) silicon monoxide powder (particle diameter is 100 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; because silicon monoxide can be reunited after high temperature sintering, so the particle diameter of the mixture finally obtained is comparatively large, this mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.In the composite material of silicon and silicon dioxide, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale 80nm.
(2) mixture is added in ball grinder, then add 4 times of ball milling pearls to the weight of mixture (large and small ball milling pearl adds according to 1: 1 ratio).Ball grinder is placed on planetary ball mill, by mixture ball milling 12 hours under the rotating speed of 300 revs/min, is become by this mixture ball milling particle diameter to be the particle of 1 micron.
(3) two hydrated stannous chlorides are dissolved in hydrochloric acid, stir and be made into a homogeneous solution in, should containing Sn
2+the pH value of acid solution be 4, wherein, Sn
2+mass percent concentration be 1wt%.
By the solution be configured to containing complexing agent soluble in water for complexing agent tartaric acid.
To be added drop-wise to above-mentioned containing Sn containing the tartaric solution of complexing agent
2+acid solution in obtain mixed solution, this mixed solution complexing agent tartaric acid and Sn
2+mass ratio be 8: 1.This mixed solution is joined in the particle of the mixture that ball milling that step (2) obtains is crossed, ultrasonic disperse obtains suspension in 10 minutes, the amount of the mixture that the ball milling that in this suspension, step (2) obtains is crossed is 20g/ml, then adds reducing agent hydroquinones, at 75 DEG C, heat 2 hours, do not stop to stir, filter, water washing, drying, obtains lithium ion battery negative material.The structure of this lithium ion battery negative material is be coated with tin outside the mixture that obtains after silicon monoxide disproportionated reaction.Wherein, the quality of tin accounts for the mass percent of lithium ion battery negative material is 1%.
The lithium ion battery negative material prepared in the present embodiment and Shanghai China fir China fir graphite cathode material FSN-1 are mixed to get mixture according to 2: 8 ratios, and by this mixture as the negative material making button cell, button cell is made according to the method preparing button cell in embodiment 1, and charge-discharge performance test is carried out to this battery: first discharge specific capacity reaches 600mAh/g, and the specific discharge capacity after 100 times that circulates is 450mAh/g.
The present embodiment provides a kind of lithium ion battery, and its negative pole comprises above-mentioned lithium ion battery negative material.
Embodiment 3
The present embodiment provides a kind of preparation method of lithium ion battery negative material, comprises the following steps:
(1) silicon monoxide powder (particle diameter is 300 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; because silicon monoxide can be reunited after high temperature sintering, so the particle diameter of the mixture finally obtained is comparatively large, this mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.In the composite material of silicon and silicon dioxide, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale 5nm.
(2) mixture is added in ball grinder, then add 4 times of ball milling pearls to the weight of mixture (large and small ball milling pearl adds according to 1: 1 ratio).Ball grinder is placed on planetary ball mill, by mixture ball milling 12 hours under the rotating speed of 300 revs/min, is become by this mixture ball milling particle diameter to be the particle of 5 microns.
(3) two hydrated stannous chlorides are dissolved in hydrochloric acid, stir and be made into a homogeneous solution in, should containing Sn
2+the hydrionic concentration of acid solution be 5M, wherein, Sn
2+mass percent concentration be 20wt%.
By the solution be configured to containing complexing agent soluble in water for complexing agent citric acid.
Solution containing complexing agent citric acid is added drop-wise to above-mentioned containing Sn
2+acid solution in obtain mixed solution, this mixed solution complexing agent citric acid and Sn
2+mass ratio be 25: 1.This mixed solution is joined in the particle of the mixture that ball milling that step (2) obtains is crossed, ultrasonic disperse obtains suspension in 10 minutes, and the amount of the mixture that the ball milling that in this suspension, step (2) obtains is crossed is 5g/ml, then the mixture adding reducing agent sodium phosphite and hydroquinones (wherein, the mass ratio of sodium phosphite and hydroquinones is 1: 1), at 90 DEG C, heat 0.5 hour, do not stop to stir, filter, water washing, dry, obtain lithium ion battery negative material.The structure of this lithium ion battery negative material is be coated with tin outside the mixture that obtains after silicon monoxide disproportionated reaction.Wherein, the quality of tin accounts for the mass percent of lithium ion battery negative material is 30%.
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 reaches 1431mAh/g, and the specific discharge capacity after 100 times that circulates is 715mAh/g.
The present embodiment provides a kind of lithium ion battery, and its negative pole comprises above-mentioned lithium ion battery negative material.
Embodiment 4
The present embodiment provides a kind of preparation method of lithium ion battery negative material, comprises the following steps:
(1) silicon monoxide powder (particle diameter is 800 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; because silicon monoxide can be reunited after high temperature sintering, so the particle diameter of the mixture finally obtained is comparatively large, this mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.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.
(2) mixture is added in ball grinder, then add 4 times of ball milling pearls to the weight of mixture (large and small ball milling pearl adds according to 1: 1 ratio).Ball grinder is placed on planetary ball mill, by mixture ball milling 12 hours under the rotating speed of 300 revs/min, is become by this mixture ball milling particle diameter to be the particle of 10 microns.
(3) two hydrated stannous chlorides are dissolved in hydrochloric acid, stir and be made into a homogeneous solution in, should containing Sn
2+the pH value of acid solution be 6, wherein, Sn
2+mass percent concentration be 5wt%.
By mixture (wherein, the mass ratio of thiocarbamide and citric acid is 1: the 1) solution be configured to containing complexing agent soluble in water of complexing agent thiocarbamide and citric acid.
The solution of the mixture containing complexing agent thiocarbamide and citric acid is added drop-wise to above-mentioned containing Sn
2+acid solution in obtain mixed solution, the mixture of this mixed solution complexing agent thiocarbamide and citric acid and Sn
2+mass ratio be 16: 1.This mixed solution is joined in the particle of the mixture that ball milling that step (2) obtains is crossed, ultrasonic disperse obtains suspension in 10 minutes, the amount of the mixture that the ball milling that in this suspension, step (2) obtains is crossed is 15g/ml, then adds reducing agent sodium phosphite, at 90 DEG C, heat 0.5 hour, do not stop to stir, filter, water washing, drying, obtains lithium ion battery negative material.The structure of this lithium ion battery negative material is be coated with tin outside the mixture that obtains after silicon monoxide disproportionated reaction.Wherein, the quality of tin accounts for the mass percent of lithium ion battery negative material is 20%.
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 reaches 984mAh/g, and the specific discharge capacity after 100 times that circulates is 546mAh/g.
The present embodiment provides a kind of lithium ion battery, and its negative pole comprises above-mentioned lithium ion battery negative material.
Embodiment 5
The present embodiment provides a kind of preparation method of lithium ion battery negative material, comprises the following steps:
(1) silicon monoxide powder (particle diameter is 500 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; because silicon monoxide can be reunited after high temperature sintering, so the particle diameter of the mixture finally obtained is comparatively large, this mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.In the composite material of silicon and silicon dioxide, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale 25nm.
(2) mixture is added in ball grinder, then add 4 times of ball milling pearls to the weight of mixture (large and small ball milling pearl adds according to 1: 1 ratio).Ball grinder is placed on planetary ball mill, by mixture ball milling 12 hours under the rotating speed of 300 revs/min, is become by this mixture ball milling particle diameter to be the particle of 6 microns.
(3) two hydrated stannous chlorides are dissolved in hydrochloric acid, stir and be made into a homogeneous solution in, should containing Sn
2+the hydrionic concentration of acid solution be 4M, wherein, Sn
2+mass percent concentration be 30wt%.
By the solution be configured to containing complexing agent soluble in water for complexing agent thiocarbamide.
Solution containing complexing agent thiocarbamide is added drop-wise to above-mentioned containing Sn
2+acid solution in obtain mixed solution, this mixed solution complexing agent thiocarbamide and Sn
2+mass ratio be 20: 1.This mixed solution is joined in the particle of the mixture that ball milling that step (2) obtains is crossed, ultrasonic disperse obtains suspension in 10 minutes, the amount of the mixture that the ball milling that in this suspension, step (2) obtains is crossed is 30g/ml, then adds reducing agent hydroquinones, at 70 DEG C, heat 3 hours, do not stop to stir, filter, water washing, drying, obtains lithium ion battery negative material.The structure of this lithium ion battery negative material is be coated with tin outside the mixture that obtains after silicon monoxide disproportionated reaction.Wherein, the quality of tin accounts for the mass percent of lithium ion battery negative material is 10%.
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 reaches 1323mAh/g, and the specific discharge capacity after 100 times that circulates is 672mAh/g.
The present embodiment provides a kind of lithium ion battery, and its negative pole comprises above-mentioned lithium ion battery negative material.
Embodiment 6
The present embodiment provides a kind of lithium ion battery, its negative pole contains lithium ion battery negative material described in the above embodiments 1 ~ 5 and graphite, wherein, the quality of lithium ion battery negative material accounts for 20% of the mixture gross mass of lithium ion battery negative material and graphite.
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 lithium ion battery negative material, is characterized in that, its structure is be coated with tin outside the mixture that obtains after silicon monoxide disproportionated reaction, and in described mixture, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale.
2. lithium ion battery negative material according to claim 1, is characterized in that, the particle diameter of described silicon monoxide is 100 ~ 800 orders, and the particle diameter of described silicon is 1 ~ 50nm.
3. lithium ion battery negative material according to claim 1, is characterized in that, the mass percent that described tin accounts for described lithium ion battery negative material is 1 ~ 30%.
4. a preparation method for the lithium ion battery negative material described in claims 1 to 3 any one, is characterized in that, comprises the following steps:
(1) silicon monoxide generation disproportionated reaction, obtains mixture;
(2) outer zinc-plated at described mixture, obtain lithium ion battery negative material.
5. the preparation method of lithium ion battery negative material according to claim 4, it is characterized in that, between described step (1) and described step (2), also comprise step (i): step (1) described mixture is worn into the particle that particle diameter is 0.1 ~ 10 micron.
6. the preparation method of lithium ion battery negative material according to claim 4, is characterized in that, described in described step (1), the temperature of silicon monoxide disproportionated reaction is 700 ~ 1200 DEG C, and the time of described disproportionated reaction is 0.5 ~ 24 hour.
7. the preparation method of lithium ion battery negative material according to claim 4, is characterized in that, described step (2) at the outer zinc-plated concrete grammar of described mixture is: join the solution containing complexing agent containing Sn
2+acid solution in obtain mixed solution, the more described mixture that this mixed solution and described step (1) obtain is mixed to get suspension, at 50 ~ 90 DEG C, heats 0.5 ~ 4 hour, then add can by described Sn
2+the reducing agent of reduction.
8. the preparation method of lithium ion battery negative material according to claim 7, is characterized in that, described containing Sn
2+acid solution in Sn
2+mass percent concentration be 1 ~ 30wt%;
Complexing agent described in described mixed solution and described Sn
2+mass ratio be (8:1) ~ (25:1);
Described complexing agent is one or more in thiocarbamide, citric acid, tartaric acid;
Described reducing agent is sodium phosphite and/or hydroquinones.
9. the preparation method of lithium ion battery negative material according to claim 7, is characterized in that, the amount of the described mixture that the described step (1) in suspension described in described step (2) obtains is 5 ~ 30g/ml.
10. a lithium ion battery, is characterized in that, its negative pole comprises the lithium ion battery negative material described in claims 1 to 3 any one.
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