CN115692612A - Tin-carbon negative electrode material and preparation method thereof - Google Patents
Tin-carbon negative electrode material and preparation method thereof Download PDFInfo
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- QWJYDTCSUDMGSU-UHFFFAOYSA-N [Sn].[C] Chemical compound [Sn].[C] QWJYDTCSUDMGSU-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007773 negative electrode material Substances 0.000 title description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000011888 foil Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 47
- 239000000843 powder Substances 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 14
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 12
- 239000010405 anode material Substances 0.000 claims description 12
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 12
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002028 Biomass Substances 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical group Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000012790 adhesive layer Substances 0.000 claims description 2
- 229940072056 alginate Drugs 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 235000013808 oxidized starch Nutrition 0.000 claims description 2
- 239000001254 oxidized starch Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 239000005539 carbonized material Substances 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 9
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 6
- 229910052708 sodium Inorganic materials 0.000 abstract description 6
- 239000011734 sodium Substances 0.000 abstract description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 229910000905 alloy phase Inorganic materials 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 230000008595 infiltration Effects 0.000 abstract 1
- 238000001764 infiltration Methods 0.000 abstract 1
- 230000002427 irreversible effect Effects 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 229910021385 hard carbon Inorganic materials 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 239000010902 straw Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 230000001788 irregular Effects 0.000 description 5
- 239000003273 ketjen black Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- GMACPFCYCYJHOC-UHFFFAOYSA-N [C].C Chemical compound [C].C GMACPFCYCYJHOC-UHFFFAOYSA-N 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- JETSKDPKURDVNI-UHFFFAOYSA-N [C].[Ca] Chemical compound [C].[Ca] JETSKDPKURDVNI-UHFFFAOYSA-N 0.000 description 1
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical compound [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 provides a tin-carbon cathode material and a preparation method thereof, wherein the tin-carbon cathode material comprises a metal foil, a conductive bonding layer and tin-carbon core ring composite active holes, more than one tin elementary substance structure is embedded into the surface of each tin-carbon core ring composite active hole, and every two adjacent tin elementary substance structures are arranged at equal intervals. The tin-carbon cathode material is low in preparation cost, a tin-carbon core ring structure is formed in the tin carbon, and the tin-carbon structure in the hole has extremely strong adsorbability on sodium ions. According to the negative electrode designed by the invention, the tin simple substance is filled in the inner surface of the hole of the core ring, wherein sodium and tin can form an alloy phase, a metastable state film is formed after baking, and the metastable state film can reach a stable state after the battery is charged and discharged and activated, so that irreversible capacity loss is favorably reduced, the first effect of the battery is improved, meanwhile, the tin-carbon core ring structure provides an electrolyte infiltration channel, and the volume effect of a tin-carbon material can be buffered, so that the cycle service life of the sodium ion battery can be greatly prolonged.
Description
Technical Field
The invention belongs to the technical field of sodium batteries, and particularly relates to a tin-carbon negative electrode material and a preparation method thereof.
Background
In recent years, due to the highly developed photovoltaic power generation and the great popularization of the water power generation, the demand for energy storage is increased rapidly, and the electrochemical energy storage is a relatively effective energy storage mode which is recognized at present. The lithium battery is the most concerned new energy at present, and the lithium battery is widely applied and researched all the time, so that the invention and the preparation of the lithium cobaltate and the ternary lithium battery change the rhythm of production and life of people at present. However, due to the increasing price and the high cost, and the large demand of energy storage, the lithium battery has low suitability for energy storage, so that the sodium ion battery similar to the lithium ion battery in working principle is widely concerned.
The extremely abundant sodium element reserves bring extremely low cost, the comprehensive cost performance is higher, and the sodium ion battery has wide prospect. Sodium ion batteries have not developed much attention for many years because they have a slightly lower energy density than lithium ion batteries. Meanwhile, in terms of materials, research and development of some anode materials basically meet the application requirements, but the practicability of the sodium-ion battery is still restricted by the cathode material.
At present, hard carbon materials are considered as the most promising sodium battery negative electrode materials in the sodium battery negative electrode materials, and firstly, the hard carbon materials can show electrochemical performance close to that of a graphite negative electrode of a lithium battery and have stable performance; and secondly, the high-temperature treatment energy consumption and the temperature are low, the raw materials are rich and easy to obtain, and the sodium insertion amount is high. However, the hard carbon has low specific capacity and the first round charge-discharge efficiency is lower than that of graphite. Therefore, how to improve the electrochemical performance of the hard carbon material is a problem to be solved urgently.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a tin-carbon anode material and a preparation method thereof, and the technical scheme adopted by the invention is as follows: the tin-carbon cathode material comprises a metal foil, a conductive bonding layer and tin-carbon core ring composite active holes, wherein more than one tin elementary substance structure is embedded into the surface of each tin-carbon core ring composite active hole, and every two adjacent tin elementary substance structures are arranged at equal intervals.
Preferably, the tin-carbon core ring composite active pores are in a porous sphere layer structure, and the total volume of the tin-carbon core ring composite active pores is 62-75% of the volume of the inner homogeneous region of the tin-carbon core ring.
Preferably, the conductive adhesive layer has a rhombic or rectangular grid structure composed of a polymer-coated conductive agent and an adhesive and having one or more lengths × widths = (2 to 15) mmx (2 to 15) mm.
Preferably, the conductive agent comprises at least one of conductive carbon black, carbon nanotubes or graphene; the adhesive comprises at least one of polyacrylic acid, sodium carboxymethyl cellulose, alginate or oxidized starch.
Also provided is a preparation method of the tin-carbon anode material, which comprises the following steps:
(1) Mixing the precursor fine powder raw material, tin powder and an organic solution of a catalyst, wherein a long-time rapid stirring is required in the mixing process to obtain a further pretreated fine powder raw material; the precursor fine powder raw material is obtained by crushing biomass organic materials, such as straws;
(2) Putting the pretreated fine powder raw material into a high-temperature carbonization furnace, heating at a constant heating rate, and sintering the raw material at a high temperature in an inert atmosphere;
(3) Introducing carbon source gas, and continuously carbonizing at high temperature;
(4) And cooling to room temperature to obtain the tin-carbon material.
The tin-carbon cathode material is low in preparation cost, and the formation of a tin-carbon core ring structure is realized by depositing a catalyst in raw materials and by a vapor deposition method. The tin-carbon core ring has a multilayer composite structure, the outermost layer is a stabilizer, the middle layer is a transition layer, the interior is a sheet-shaped hole structure, and tin atoms are embedded in the inner surface of the hole. The tin atoms can form an alloy phase with sodium ions, so that the electronic conductivity, specific capacity, first coulombic efficiency of the battery and the like of the material can be improved.
Preferably, the mesh number of the tin powder in the step (1) is 100 meshes, 200 meshes, 300 meshes, 400 meshes, 500 meshes, 600 meshes, 650 meshes, 700 meshes, 750 meshes, 800 meshes, 850 meshes, 900 meshes, 1000 meshes
Preferably, the mass fraction of the tin powder in the fine powder raw material in the step (1) is 0.5 to 5wt%, such as 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%, 3wt%, 3.5wt%, 4.0wt%, 4.5wt%, or 5.0 wt%.
In the invention, if the mixing time of the precursor fine powder raw material, the catalyst and the tin powder is too short, the catalyst and the tin are difficult to enter the material, the subsequent formation of a tin-carbon core ring structure is not facilitated, but the soaking time is too long, and the preparation process time is longer.
The invention has the following beneficial effects: the tin-carbon cathode material is low in preparation cost, a tin-carbon core ring structure is formed in the tin carbon, the electronic conductivity of the material, the specific capacity of a battery and the first coulombic efficiency are finally improved, and the material has the characteristics of high first effect and long service life; the cathode plate made of the material has strong cohesiveness with a current collector, good electrolyte wettability, high first effect and long cycle life.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the following examples.
Example 1
Cleaning and drying 100g of straws, crushing the straws by using a ball mill for 300r/min to obtain coarse powder, and screening the coarse powder to obtain a biomass precursor fine powder raw material with the particle size of 100-200 meshes. And mixing the precursor fine powder raw material, a tetrahydrofuran solution with the nickel chloride mass fraction of 1 wt% and 100-mesh tin powder, and soaking for 1h to obtain a further pretreated fine powder raw material. The soaking time can be adjusted by a person skilled in the art according to the actual situation, and is preferably 1 to 8 hours.
And (3) putting the pretreated fine powder raw material into a muffle furnace for heat treatment at 300 ℃ for 2h. And (3) putting the raw material after the heat treatment into a high-temperature carbonization furnace, heating to 1000 ℃ at the heating rate of 3 ℃/min, and sintering the raw material at high temperature in an inert atmosphere for 3h. And introducing methane carbon source gas, firing at the high temperature of 800 ℃ for 1 hour, and cooling to room temperature to obtain the carbon material with irregular block shape, namely the high-capacity tin-carbon material with the tin-carbon core ring structure on the surface structure.
The tin-carbon negative electrode material is assembled into a button cell, and the mass ratio of the tin-carbon negative electrode material to CMC (sodium carboxymethyl cellulose) and Ketjen black of the raw materials of the button cell is 8:1:1. and carrying out electrochemical performance detection on the button cell.
Example 2
100g of straw is cleaned and dried, and then is crushed by a ball mill at 300r/min to obtain coarse powder. Screening the coarse powder to obtain the biomass precursor fine powder raw material with the particle size of 100-200 meshes. And mixing the precursor fine powder raw material, a tetrahydrofuran solution with 1 wt% of ferric chloride in mass fraction and 200-mesh tin powder, and soaking for 2 hours to obtain a further pretreated fine powder raw material. And (3) putting the pretreated fine powder raw material into a muffle furnace for heat treatment at 300 ℃ for 2h. And (3) putting the raw material subjected to heat treatment into a high-temperature carbonization furnace, heating to 1000 ℃ at the heating rate of 3 ℃/min, and sintering the raw material at high temperature in an inert atmosphere for 3 hours. And introducing methane carbon source gas, firing at the high temperature of 800 ℃ for 1 hour, and cooling to room temperature to obtain the carbon material with irregular block shape, namely the high-capacity tin-carbon material with the tin-carbon core ring structure on the surface structure.
The tin-carbon negative electrode material is assembled into a button cell, and the mass ratio of the raw materials of the button cell to CMC (sodium carboxymethyl cellulose) and Ketjen black is 8:1:1. and carrying out electrochemical performance detection on the button cell.
Example 3
100g of straws are cleaned and dried, and then are crushed by a ball mill at 300r/min to obtain coarse powder. Screening the coarse powder to obtain the biomass precursor fine powder raw material with the particle size of 100-200 meshes. And mixing the precursor fine powder raw material, a tetrahydrofuran solution with the nickel chloride mass fraction of 1 wt% and 300-mesh tin powder, and soaking for 1h to obtain a further pretreated fine powder raw material. And (3) putting the pretreated fine powder raw material into a muffle furnace for heat treatment at 300 ℃ for 2h. And (3) putting the raw material subjected to heat treatment into a high-temperature carbonization furnace, heating to 1000 ℃ at the heating rate of 3 ℃/min, and sintering the raw material at high temperature in an inert atmosphere for 3 hours. And introducing methane carbon source gas, firing at the high temperature of 800 ℃ for 1 hour, and cooling to room temperature to obtain the carbon material with irregular block shape, namely the high-capacity tin-carbon material with the tin-carbon core ring structure on the surface structure.
The tin-carbon negative electrode material is assembled into a button cell, and the mass ratio of the tin-carbon negative electrode material to CMC (sodium carboxymethyl cellulose) and Ketjen black of the raw materials of the button cell is 8:1:1. and carrying out electrochemical performance detection on the button cell.
Example 3
100g of straws are cleaned and dried, and then are crushed by a ball mill at 300r/min to obtain coarse powder. Screening the coarse powder to obtain the biomass precursor fine powder raw material with the particle size of 100-200 meshes. And mixing the precursor fine powder raw material, a tetrahydrofuran solution with the nickel chloride mass fraction of 1 wt% and 400-mesh tin powder, and soaking for 1h to obtain a further pretreated fine powder raw material. And (3) putting the pretreated fine powder raw material into a muffle furnace for heat treatment at 300 ℃ for 2h. And (3) putting the raw material subjected to heat treatment into a high-temperature carbonization furnace, heating to 1000 ℃ at the heating rate of 3 ℃/min, and sintering the raw material at high temperature in an inert atmosphere for 3 hours. And introducing methane carbon source gas, firing at the high temperature of 800 ℃ for 1 hour, and cooling to room temperature to obtain the carbon material with irregular block shape, namely the high-capacity tin-carbon material with the tin-carbon core ring structure on the surface structure.
The tin-carbon negative electrode material is assembled into a button cell, and the mass ratio of the tin-carbon negative electrode material to CMC (sodium carboxymethylcellulose) and Ketjen black of the button cell is 8:1:1. and carrying out electrochemical performance detection on the button cell.
Example 4
The tin powder mesh number of the embodiment 1 is changed into 500 meshes to prepare the tin-carbon cathode material, and the other preparation methods and parameters are kept consistent.
Example 5
The tin powder mesh number of the embodiment 1 is changed into 600 meshes to prepare the tin-carbon cathode material, and the other preparation methods and parameters are kept consistent.
Comparative example 1
100g of straws are cleaned and dried, and are crushed by a ball mill at 300r/min to obtain coarse powder. Sieving the coarse powder to obtain the biomass precursor fine powder raw material with the particle size of 100-200 meshes. And mixing the pretreated fine powder raw material with a tetrahydrofuran solution with the mass fraction of ferric chloride of 1 wt%, and soaking for 2 hours to obtain a further pretreated fine powder raw material. And (3) putting the pretreated fine powder raw material into a muffle furnace for heat treatment at 300 ℃ for 1h. And (3) putting the raw material subjected to heat treatment into a high-temperature carbonization furnace, heating to 1000 ℃ at the heating rate of 3 ℃/min, and sintering the raw material at high temperature in an inert atmosphere for 3 hours. And cooling to room temperature to obtain the hard carbon material with irregular blocky appearance.
The hard carbon negative electrode material is assembled into a button cell, and the mass ratio of the hard carbon negative electrode material to CMC (sodium carboxymethyl cellulose) and Ketjen black is 8:1:1. and carrying out electrochemical performance detection on the button cell.
Comparative example 2
The tin powder added in the comparative example 1 is changed into phosphorus powder to prepare the phosphorus-carbon anode material, and the other preparation methods and parameters are kept consistent.
Comparative example 3
The tin powder added in the comparative example 1 is changed into calcium powder to prepare the calcium-carbon anode material, and the other preparation methods and parameters are kept consistent.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (7)
1. A tin-carbon anode material characterized in that: the tin-carbon core ring composite active hole comprises a metal foil, a conductive bonding layer and tin-carbon core ring composite active holes, wherein more than one tin elementary substance structure is embedded into the surface of each tin-carbon core ring composite active hole, and every two adjacent tin elementary substance structures are arranged at equal intervals.
2. The tin-carbon anode material according to claim 1, wherein: the tin-carbon core ring composite active holes are in a porous ball layer structure, and the total volume of the tin-carbon core ring composite active holes is 62-75% of the volume of the inner homogeneous area of the tin-carbon core ring.
3. The tin-carbon anode material according to claim 1, wherein: the conductive adhesive layer is a rhombic or rectangular grid structure which is composed of a polymer-coated conductive agent and an adhesive and has more than one length multiplied by width (= (2 to 15) mmx (2 to 15) mm.
4. The tin-carbon anode material according to claim 3, wherein: the conductive agent comprises at least one of conductive carbon black, carbon nanotubes or graphene.
5. The tin-carbon anode material according to claim 3, wherein: the adhesive comprises at least one of polyacrylic acid, sodium carboxymethyl cellulose, alginate or oxidized starch.
6. A method for preparing the tin-carbon anode material as defined in any one of claims 1 to 5, comprising the preparation steps of:
(1) Mixing the precursor fine powder raw material, tin powder and an organic solution of a catalyst, and quickly mixing and stirring in the mixing process to obtain a further pretreated fine powder raw material; the precursor fine powder raw material is obtained by crushing a biomass material;
(2) Putting the pretreated fine powder raw material in the step (1) into a high-temperature carbonization furnace, heating at a constant heating rate, and sintering the raw material at a high temperature in an inert atmosphere;
(3) Introducing carbon source gas, and continuously carbonizing at high temperature;
(4) And (4) cooling the carbonized material obtained in the step (3) to room temperature to obtain the tin-carbon material.
7. The preparation method of the tin-carbon anode material as claimed in claim 6, wherein in the step (1), the mesh number of the tin powder is 100-900 meshes, and the mixing and stirring speed is 200-300 r/min.
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| US20130344394A1 (en) * | 2011-03-10 | 2013-12-26 | Shanghai Jiao Tong University | Tin carbon composite, method for preparing same, battery negative electrode component comprising same, and battery having the negative electrode component |
| CN104577079A (en) * | 2014-12-22 | 2015-04-29 | 江西正拓新能源科技股份有限公司 | Method for preparing tin-carbon composite negative electrode material |
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