CN117673302A - Sulfur anode material and preparation method thereof, anode slurry and slurry mixing method thereof - Google Patents
Sulfur anode material and preparation method thereof, anode slurry and slurry mixing method thereof Download PDFInfo
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- 239000002002 slurry Substances 0.000 title claims abstract description 82
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 70
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000011593 sulfur Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 238000002156 mixing Methods 0.000 title claims abstract description 41
- 239000010405 anode material Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000006256 anode slurry Substances 0.000 title claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 239000010949 copper Substances 0.000 claims abstract description 32
- 239000010406 cathode material Substances 0.000 claims abstract description 31
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 20
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001450 anions Chemical class 0.000 claims abstract description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000000129 anionic group Chemical group 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 98
- 239000000463 material Substances 0.000 claims description 33
- 239000007773 negative electrode material Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000011267 electrode slurry Substances 0.000 claims description 26
- 239000011230 binding agent Substances 0.000 claims description 20
- 239000006258 conductive agent Substances 0.000 claims description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 16
- 239000010410 layer Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- -1 Transition Metal Sulfides Chemical class 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000681 Silicon-tin Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- LQJIDIOGYJAQMF-UHFFFAOYSA-N lambda2-silanylidenetin Chemical compound [Si].[Sn] LQJIDIOGYJAQMF-UHFFFAOYSA-N 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a sulfur anode material and a preparation method thereof, and anode slurry and a slurry mixing method thereof. Wherein the sulfur cathode material is lamellar crystalline sulfide, and has [ Cu ] 2 SbS 3 ] ‑ Two-dimensional anion layer, ethylenediamine molecule interpenetrates [ Cu ] 2 SbS 3 ] ‑ In the two-dimensional anionic layer. The preparation method of the sulfur cathode material comprises the following steps: copper powder, antimony powder, thiourea and solvent are mixed and sealed in a high-pressure container, and the mixture is heat treated for 5 to 10 days at the temperature of 140 to 180 ℃ and then cooled and washed. The sulfur cathode material is used for batteries, and has higher specific capacity, better charge and discharge rate performance and cycle stability.
Description
Technical Field
The invention relates to the technical field of energy storage instrument material preparation, in particular to a negative electrode material, and more particularly relates to a sulfur negative electrode material and a preparation method thereof, a negative electrode slurry and a slurry mixing method thereof.
Background
The negative electrode materials of conventional lithium ion batteries are typically carbon materials (natural graphite, artificial graphite, soft carbon or hard carbon) and silicon materials (silicon oxygen materials, silicon tin alloys or silicon carbon materials). In order to meet the increasing demand of clean energy, the conventional anode materials cannot meet the demand, so that it is necessary to explore new electrode materials to improve the efficiency of lithium ion batteries.
Binary Transition Metal Sulfides (TMDs) have been widely focused on the research fields of alkali metal (Li, na, K) rechargeable batteries, supercapacitors and the like due to their unique advantages of graphene-like layered structures, potential high specific capacity, rich storage of raw material elements and the like. In particular, TMDs (e.g. MX 2 In which M is selected from V, ti, zr, nb, mo, etc., and X is selected from S, se, te, etc.) have been used in lithium/sodium ion battery research. With Na and Na + Or K + In comparison with Li + (ion radius is) Far less than->And->
However, binary Transition Metal Sulfides (TMDs) have limited specific capacities, and sulfide material structures are not stable enough during charge and discharge of the battery, affecting the cycle performance of the battery.
Disclosure of Invention
Based on the above problems, the present invention aims to provide a sulfur negative electrode material and a preparation method thereof, a negative electrode slurry and a slurry mixing method thereof. The sulfur cathode material is used for batteries, and has higher specific capacity, better charge and discharge rate performance and cycle stability.
To achieve the above object, a first aspect of the present invention provides a sulfur anode material, which is a layered crystalline sulfide, having [ Cu 2 SbS 3 ] - Two-dimensional anion layer, ethylenediamine molecule interpenetrates with [ Cu ] 2 SbS 3 ] - In the two-dimensional anionic layer.
Compared with the prior art, the sulfur cathode material has at least the following technical effects.
(1) Compared with binary TMDs, the sulfur cathode material provided by the invention is a ternary system. Copper and antimony are binary metal cations, and the specific capacity of the anode material is high because the reaction can reach higher specific capacity through a plurality of oxidation-reduction reactions.
(2) Cu is introduced into a ternary system sulfur-antimony material system + The stable lamellar structure can be obtained by utilizing the thiophilic property of the lithium ion battery, and the skeleton formed by the lamellar structure is relatively stable in the charge and discharge process, so that the assembled lithium ion battery has good cycle stability.
(3) Transition metal Cu + The catalyst has good electrochemical catalytic activity, can promote the intercalation/deintercalation reaction of lithium ions, and is beneficial to improving the charge and discharge rate performance and the cycle stability of the lithium ion battery.
(4) Ethylenediamine molecular interpenetration [ Cu ] 2 SbS 3 ] - In the two-dimensional anion layer, the interlayer spacing is larger, a wide path can be provided for the transportation of lithium ions, and the unique layered structure of ethylenediamine molecules can play a role in stabilizing [ Cu ] in the charge and discharge process 2 SbS 3 ] - The effect of the framework can further improve the cycle stability of the cathode material.
As one embodiment of the present invention, the [ Cu ] 2 SbS 3 ] - The two-dimensional anion layer is ten-membered [ Cu ] 3 Sb 2 S 8 ]Ring and six-membered [ Cu ] 2 SbS 3 ]Ring [010 ]]Two single layers formed by the plane are connected with each other to form a two-dimensional structure.
As one technical scheme of the invention, the chemical formula is [ C 2 N 2 H 10 ] 0.5 Cu 2 SbS 3 ·H 2 O。
The second aspect of the invention provides a method for preparing a sulfur cathode material, comprising the steps of: copper powder, antimony powder, thiourea and solvent are mixed and sealed in a high-pressure container, and the mixture is heat treated for 5 to 10 days at the temperature of 140 to 180 ℃ and then cooled and washed.
The preparation method of the sulfur cathode material adopts a solvothermal synthesis method. Compared with other preparation methods, the solvent thermal synthesis method can obtain uniformly dispersed nano particles, and can improve the charge and discharge rate performance and the cycle stability of the material. In addition, the solvothermal synthesis method can control the morphology, structure and electrochemical performance of the material by regulating and controlling the reaction condition and adding proper additives, and has higher controllability and flexibility. In addition, compared with the traditional lithium ion battery anode material (such as graphite, etc.), the sulfur anode material has less waste generated in the preparation process, and the material has good reproducibility and recyclability and has less influence on the environment.
As a technical scheme of the invention, the mass ratio of the copper powder to the antimony powder to the thiourea to the solvent is 1-1.1:1:15-25:100-150.
As an aspect of the present invention, the solvent includes ethanol and/or water.
The third aspect of the invention provides a negative electrode slurry, which comprises, by mass, 80-95 parts of a negative electrode material, 1-10 parts of a conductive agent, 1-10 parts of a binder and 45-65 parts of a solvent, wherein the binder at least comprises CMC, and the negative electrode material is the sulfur negative electrode material prepared by the sulfur negative electrode material or the preparation method of the sulfur negative electrode material. The negative electrode slurry has better stability and dispersibility.
As an aspect of the present invention, the conductive agent is at least one selected from the group consisting of conductive carbon black, acetylene black, graphene and carbon nanotubes, the binder further comprises SBR, and the solvent is selected from the group consisting of water.
The fourth aspect of the invention provides a slurry mixing method of negative electrode slurry, which comprises the following steps.
(1) Vacuum stirring the conductive agent, the negative electrode material and 30-70 wt.% of CMC in a double-planetary stirring kettle to obtain a mixed material;
(2) Adding a first part of the solvent into the mixed material and mixing to obtain first slurry;
(3) Adding the rest part of CMC into the first slurry, and mixing again to obtain second slurry;
(4) Adding a second part of the solvent into the second slurry, and mixing to obtain a third slurry;
(5) And after the stirring frequency is increased to stir the third slurry, adding the rest of the solvent and the binder to stir, adjusting the solid content of the slurry to 35-55%, reducing the stirring speed, vacuumizing and stirring, and discharging the gas in the slurry.
The sulfur cathode material is a nano system, and CMC is added in sections in the mixed slurry to avoid slurry gelation. In addition, the conductive agent, the cathode material and CMC are subjected to vacuum stirring in a double-planetary stirring kettle to be dry-mixed, so that the surface of the cathode material can be coated with a CNT conductive agent layer, and the final lithium ion battery has good conductivity, circulation performance and safety performance. The prepared negative electrode slurry has good conductivity and dispersibility.
The invention also provides the application of the sulfur cathode material or the sulfur cathode material prepared by the preparation method of the sulfur cathode material in a lithium ion battery.
Drawings
FIG. 1 is a view showing the structure of a sulfur anode material of the present invention 2 SbS 3 ] - Schematic representation of two-dimensional anionic layer.
Fig. 2 is an XRD pattern of the sulfur anode material of the present invention.
Detailed Description
The sulfur cathode material of the invention is lamellar crystalline sulfide and has [ Cu ] 2 SbS 3 ] - Two-dimensional anion layer, ethylenediamine molecule interpenetrates [ Cu ] 2 SbS 3 ] - In the two-dimensional anionic layer. [ Cu ] 2 SbS 3 ] - The two-dimensional anion layer is ten-membered [ Cu ] 3 Sb 2 S 8 ]Ring and six-membered [ Cu ] 2 SbS 3 ]Ring [010 ]]Two single layers formed by the plane are connected with each other to form a two-dimensional structure, as shown in fig. 1. The lamellar crystalline sulfide has the chemical formula [ C ] 2 N 2 H 10 ] 0.5 Cu 2 SbS 3 ·H 2 O, the interlayer spacing isWhile Li is + Radius is->The larger interlayer spacing of the layered crystalline sulfide provides a broad path for lithium ion transport. The lamellar crystalline sulfide has larger interlayer spacing and structural stability, so that the lamellar crystalline sulfide can be used in a lithium ion battery, and the charge and discharge rate performance and the cycle stability of the lithium ion battery can be greatly improved.
The sulfur cathode material of the invention can be prepared by adopting a solvothermal synthesis method, and the preparation method comprises the following steps: copper powder, antimony powder, thiourea and solvent are mixed and sealed in a high-pressure container, and the mixture is heat treated for 5 to 10 days at the temperature of 140 to 180 ℃ and then cooled and washed. Wherein the mass ratio of the copper powder to the antimony powder to the thiourea to the solvent is 1-1.1:1:15-25:100-150. The solvent comprises ethanol and/or water. The preparation raw materials can be stirred uniformly and then placed in a heat-resistant glass tube, and the heat-resistant glass tube is sealed under the air atmosphere and then placed in a stainless steel autoclave for heat treatment. The conditions for the heat treatment are preferably 160℃and 7d. Washing with ethanol for several times after heat treatment to obtain orange rod-like crystal, i.e. lamellar crystalline sulfide.
The sulfur cathode material can be used as a cathode material of a lithium ion battery, and a positive electrode material of the sulfur cathode material can be a conventional positive electrode material, such as a lithium cobalt oxide system material, a lithium iron phosphate system material, a lithium nickel cobalt manganese oxide system material, a lithium nickel cobalt aluminum acid system material or the like. The electrolyte may be a conventional electrolyte, and may include lithium salts, nonaqueous organic solvents, and conductive agents.
The sulfur cathode material can be used for cathode materials of lithium ion batteries. The preparation raw materials of the anode slurry can comprise 80-95 parts of sulfur anode material, 1-10 parts of conductive agent, 1-10 parts of binder and 45-65 parts of solvent. The sulfur negative electrode material may be, but is not limited to, 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 87 parts, 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts. The sulfur negative electrode material can be the lamellar crystalline sulfide, and has [ Cu 2 SbS 3 ] - Two-dimensional anion layer, ethylenediamine molecule interpenetrates [ Cu ] 2 SbS 3 ] - In the two-dimensional anionic layer. [ Cu ] 2 SbS 3 ] - The two-dimensional anion layer is ten-membered [ Cu ] 3 Sb 2 S 8 ]Ring and six-membered [ Cu ] 2 SbS 3 ]Ring [010 ]]Two single layers formed by the plane are connected with each other to form a two-dimensional structure. The chemical formula of the lamellar crystalline sulfide is [ C 2 N 2 H 10 ] 0.5 Cu 2 SbS 3 ·H 2 O. The conductive agent may be, but is not limited to, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts. The conductive agent is at least one selected from conductive carbon black, acetylene black, graphene and carbon nanotubes. The binder may be, but is not limited to, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts. Binders include CMC and SBR. The solvent may be, but is not limited to, 45 parts, 47 parts, 49 parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 61 parts, 63 parts, 65 parts, and the solvent is selected from water.
Because the sulfur cathode material is a nano material and is easy to agglomerate, the slurry mixing method can adopt the following steps to avoid material agglomeration and slurry gelation.
(1) Vacuum stirring the conductive agent, the negative electrode material and 30-70 wt.% CMC in a double-planetary stirring kettle to obtain a mixed material;
(2) Adding a first part of solvent into the mixed material, and mixing to obtain first slurry;
(3) Adding the rest CMC into the first slurry, and mixing to obtain a second slurry;
(4) Adding a second part of solvent into the second slurry, and mixing to obtain a third slurry;
(5) After the stirring frequency is increased to stir the third slurry, adding the rest solvent and the binder to stir, adjusting the solid content of the slurry to 35-55%, reducing the stirring speed, vacuumizing and stirring, and removing the gas in the slurry.
Wherein in the step (1), the revolution frequency of stirring is 15-40 Hz, the rotation frequency is 5-30 Hz, and the time is 20-90 min. In the step (2), the solvent of the first part can be 20-80 wt.%, the revolution frequency of the double-planetary stirring kettle is 15-40 Hz, the rotation frequency is 5-30 Hz, and the time is 60-120 min during mixing. The revolution frequency of the double planetary stirring kettle in the step (3) is 15-40 Hz, the rotation frequency is 5-30 Hz, and the time is 10-30 min. In the step (4), the solvent in the second part can be 15-75 wt%, the revolution frequency of the double-planetary stirring kettle is 15-40 Hz, the rotation frequency is 5-30 Hz, and the time is 5-10 min during mixing. In the step (5), the rotation frequency is increased to 25-45 Hz, the stirring time is 60-90 min, and the vacuum degree is less than or equal to-0.08 MPa. The revolution frequency of the double-planetary stirring kettle is 15-40 Hz, the rotation frequency is 15-25 Hz, and the time is 30-60 min when the residual solvent and the binder are added for stirring. The revolution frequency of the double-planetary stirring kettle is 8-15 Hz, the rotation frequency is 0, and the time is 20-60 min during vacuumizing stirring.
After the negative electrode slurry is prepared by adopting the slurry mixing method, the copper foil is coated, dried, rolled and die-cut to prepare the negative electrode plate. The positive plate can also be prepared by preparing positive electrode materials, conductive agents, binders and solvents into positive electrode slurry, and then coating, drying, rolling and die-cutting the positive electrode slurry on aluminum foil.
For a better description of the objects, technical solutions and advantageous effects of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation of the method is a further explanation of the present invention and should not be taken as limiting the present invention.
(1) A first part: preparation of sulfur cathode material
Example 1
The embodiment is a preparation of a sulfur anode material, comprising the steps of: mixing copper powder, antimony powder, thiourea, 99.8wt.% of anhydrous methanol and water according to a mass ratio of 1:1:20:37:83, sealing in a high-pressure container, performing heat treatment at 160 ℃ for 7 days, cooling, washing with ethanol for several times to obtain orange rod-shaped crystals, and obtaining a sulfur anode material 1#, wherein the chemical formula is [ C ] 2 N 2 H 10 ] 0.5 Cu 2 SbS 3 ·H 2 O。
The XRD detection was performed on the sulfur negative electrode material 1# as shown in fig. 2, which is a powder diffraction pattern of the material and an XRD powder diffraction pattern calculated from a single crystal structure simulation. The position of its main diffraction peak (2θ=10°) is substantially consistent with the result of the single crystal data fitting. It is known that the material is pure phase and has a layered structure.
Example 2
The embodiment is a preparation of a sulfur anode material, comprising the steps of: mixing copper powder, antimony powder, thiourea, 99.8wt.% of anhydrous methanol and water according to a mass ratio of 1.1:1:25:45:70, sealing in a high-pressure container, performing heat treatment at 180 ℃ for 8 days, cooling, and washing with ethanol for several times to obtain orange rod-shaped crystals, thereby obtaining a sulfur negative electrode material No. 2.
Example 3
The embodiment is a preparation of a sulfur anode material, comprising the steps of: copper powder, antimony powder, thiourea and water are mixed according to a mass ratio of 1:1:18:100, then the mixture is sealed in a high-pressure container, heat treatment is carried out for 6d at 150 ℃, cooling is carried out, and orange rod-shaped crystals are obtained after washing by ethanol for several times, thus obtaining a sulfur negative electrode material 3#.
Example 4
The embodiment is a preparation of a sulfur anode material, comprising the steps of: with 10vol.% hydrogen sulfide in H 2 S-H 2 The mixed gas carries out vulcanization on the ammonium tetrathiomolybdate, the vulcanization temperature is 325 ℃, the time is 3 hours, and the MoS is obtained after the vulcanization 2 Marked as sulfur anode material # 4.
Example 5
The embodiment is a preparation of a sulfur anode material, comprising the steps of: weighing 0.830g of potassium carbonate, 1.068g of tin powder and 0.962g of sulfur powder, mixing, grinding in a mortar for 10min to uniformly mix, putting the uniformly mixed powder in a 28mL Polytetrafluoroethylene (PTFE) reaction kettle, adding 0.5mL of deionized water, heating in a 220 ℃ oven for 15h, cooling to room temperature, and washing a sample with water to obtain yellow rod-shaped crystals which are crystalline sulfide K 1.92 Sn 3.04 S 7.04 Marked as sulfur anode material # 5.
(2) A second part: preparation of negative electrode slurry
Example 6
This example is a preparation of a negative electrode slurry, the preparation raw materials including 80 parts of a sulfur negative electrode material, 5 parts of a conductive agent, 5 parts of a binder and 55 parts of a solvent, and the preparation method including the following steps.
(1) The carbon nanotube, sulfur cathode material 1# and 50wt.% CMC were vacuum stirred in a double planetary stirring tank (revolution frequency of stirring was 20Hz, rotation frequency was 20Hz, time was 60 min) to obtain a mixed material.
(2) 50wt.% of water is added into the mixed material to obtain a first slurry, and the revolution frequency of the double-planetary stirring kettle is 20Hz, the rotation frequency is 20Hz and the time is 100min during mixing.
(3) Adding the rest CMC into the first slurry, and mixing to obtain a second slurry, wherein the revolution frequency of the double-planetary stirring kettle is 25Hz, the rotation frequency is 15Hz, and the time is 20min.
(4) And adding 30wt.% of water into the second slurry, and mixing to obtain a third slurry, wherein the revolution frequency of the double-planetary stirring kettle is 25Hz, the rotation frequency is 25Hz, and the time is 10min.
(5) Raising the stirring frequency to 40Hz, opening vacuum to less than or equal to-0.08 MPa, stirring the third slurry for 60min, adding 20wt.% of water and SBR, stirring (revolution frequency of the double-planetary stirring kettle is 40Hz, rotation frequency is 15Hz, time is 40min, and the solid content of the slurry is 50 percent), reducing revolution frequency of the double-planetary stirring kettle to 10Hz, rotation frequency is 0, vacuumizing and stirring for 45min, and removing gas in the slurry to obtain negative electrode slurry 1#.
Example 7
This example is a preparation of a negative electrode slurry, the preparation raw materials including 80 parts of a sulfur negative electrode material, 5 parts of a conductive agent, 5 parts of a binder and 55 parts of a solvent, and the preparation method including the following steps.
(1) The carbon nanotube, sulfur cathode material 2# and 50wt.% CMC were vacuum stirred in a double planetary stirring tank (revolution frequency of stirring was 20Hz, rotation frequency was 20Hz, time was 60 min) to obtain a mixed material.
(2) 50wt.% of water is added into the mixed material to obtain a first slurry, and the revolution frequency of the double-planetary stirring kettle is 20Hz, the rotation frequency is 20Hz and the time is 100min during mixing.
(3) Adding the rest CMC into the first slurry, and mixing to obtain a second slurry, wherein the revolution frequency of the double-planetary stirring kettle is 25Hz, the rotation frequency is 15Hz, and the time is 20min.
(4) And adding 30wt.% of water into the second slurry, and mixing to obtain a third slurry, wherein the revolution frequency of the double-planetary stirring kettle is 25Hz, the rotation frequency is 25Hz, and the time is 10min.
(5) Raising the stirring frequency to 40Hz, opening vacuum to less than or equal to-0.08 MPa, stirring the third slurry for 60min, adding 20wt.% of water and SBR, stirring (revolution frequency of the double-planetary stirring kettle is 40Hz, rotation frequency is 15Hz, time is 40min, and the solid content of the slurry is 50 percent), reducing revolution frequency of the double-planetary stirring kettle to 10Hz, rotation frequency is 0, vacuumizing and stirring for 45min, and removing gas in the slurry to obtain negative electrode slurry 2#.
Example 8
This example is a preparation of a negative electrode slurry, the preparation raw materials including 80 parts of a sulfur negative electrode material, 5 parts of a conductive agent, 5 parts of a binder and 55 parts of a solvent, and the preparation method including the following steps.
(1) The carbon nanotube, sulfur cathode material 3# and 50wt.% CMC were vacuum stirred in a double planetary stirring tank (revolution frequency of stirring was 20Hz, rotation frequency was 20Hz, time was 60 min) to obtain a mixed material.
(2) 50wt.% of water is added into the mixed material to obtain a first slurry, and the revolution frequency of the double-planetary stirring kettle is 20Hz, the rotation frequency is 20Hz and the time is 100min during mixing.
(3) Adding the rest CMC into the first slurry, and mixing to obtain a second slurry, wherein the revolution frequency of the double-planetary stirring kettle is 25Hz, the rotation frequency is 15Hz, and the time is 20min.
(4) And adding 30wt.% of water into the second slurry, and mixing to obtain a third slurry, wherein the revolution frequency of the double-planetary stirring kettle is 25Hz, the rotation frequency is 25Hz, and the time is 10min.
(5) Raising the stirring frequency to 40Hz, opening vacuum to less than or equal to-0.08 MPa, stirring the third slurry for 60min, adding 20wt.% of water and SBR, stirring (revolution frequency of the double-planetary stirring kettle is 40Hz, rotation frequency is 15Hz, time is 40min, and the solid content of the slurry is 50 percent), reducing revolution frequency of the double-planetary stirring kettle to 10Hz, rotation frequency is 0, vacuumizing and stirring for 45min, and removing gas in the slurry to obtain negative electrode slurry 3#.
Example 9
This example is a preparation of a negative electrode slurry, the preparation raw materials including 90 parts of a sulfur negative electrode material, 5 parts of a conductive agent, 9 parts of a binder and 60 parts of a solvent, and the preparation method including the following steps.
(1) The carbon nanotube, sulfur cathode material 1# and 40wt.% CMC were vacuum stirred in a double planetary stirring tank (revolution frequency of stirring was 25Hz, rotation frequency was 15Hz, time was 80 min) to obtain a mixed material.
(2) 60wt.% of water is added into the mixed material to obtain a first slurry, and the revolution frequency of the double-planetary stirring kettle is 25Hz, the rotation frequency is 15Hz and the time is 80min during mixing.
(3) Adding the rest CMC into the first slurry, and mixing to obtain a second slurry, wherein the revolution frequency of the double-planetary stirring kettle is 30Hz, the rotation frequency is 15Hz, and the time is 15min.
(4) 25wt.% of water is added into the second slurry and then mixed to obtain a third slurry, wherein the revolution frequency of the double-planetary stirring kettle is 35Hz, the rotation frequency is 30Hz and the time is 10min during mixing.
(5) Raising the stirring frequency to 45Hz, opening vacuum to less than or equal to-0.08 MPa, stirring the third slurry for 60min, adding 15wt.% of water and SBR, stirring (revolution frequency of the double-planetary stirring kettle is 30Hz, rotation frequency is 20Hz, time is 40min, and the solid content of the slurry is 45 percent), reducing revolution frequency of the double-planetary stirring kettle to 10Hz, rotation frequency is 0, vacuumizing and stirring for 45min, and removing gas in the slurry to obtain negative electrode slurry 4#.
Example 10
This example is a preparation of a negative electrode slurry, the preparation raw materials including 80 parts of a sulfur negative electrode material, 5 parts of a conductive agent, 5 parts of a binder and 55 parts of a solvent, and the preparation method including the following steps.
(1) The carbon nanotube, sulfur cathode material 4# and 50wt.% CMC were vacuum stirred in a double planetary stirring tank (revolution frequency of stirring was 20Hz, rotation frequency was 20Hz, time was 60 min) to obtain a mixed material.
(2) 50wt.% of water is added into the mixed material to obtain a first slurry, and the revolution frequency of the double-planetary stirring kettle is 20Hz, the rotation frequency is 20Hz and the time is 100min during mixing.
(3) Adding the rest CMC into the first slurry, and mixing to obtain a second slurry, wherein the revolution frequency of the double-planetary stirring kettle is 25Hz, the rotation frequency is 15Hz, and the time is 20min.
(4) And adding 30wt.% of water into the second slurry, and mixing to obtain a third slurry, wherein the revolution frequency of the double-planetary stirring kettle is 25Hz, the rotation frequency is 25Hz, and the time is 10min.
(5) Raising the stirring frequency to 40Hz, opening vacuum to less than or equal to-0.08 MPa, stirring the third slurry for 60min, adding 20wt.% of water and SBR, stirring (revolution frequency of the double-planetary stirring kettle is 40Hz, rotation frequency is 15Hz, time is 40min, and the solid content of the slurry is 50 percent), reducing revolution frequency of the double-planetary stirring kettle to 10Hz, rotation frequency is 0, vacuumizing and stirring for 45min, and removing gas in the slurry to obtain negative electrode slurry 5#.
Example 11
This example is a preparation of a negative electrode slurry, the preparation raw materials including 80 parts of a sulfur negative electrode material, 5 parts of a conductive agent, 5 parts of a binder and 55 parts of a solvent, and the preparation method including the following steps.
(1) The carbon nanotube, sulfur cathode material 5# and 50wt.% CMC were vacuum stirred in a double planetary stirring tank (revolution frequency of stirring was 20Hz, rotation frequency was 20Hz, time was 60 min) to obtain a mixed material.
(2) 50wt.% of water is added into the mixed material to obtain a first slurry, and the revolution frequency of the double-planetary stirring kettle is 20Hz, the rotation frequency is 20Hz and the time is 100min during mixing.
(3) Adding the rest CMC into the first slurry, and mixing to obtain a second slurry, wherein the revolution frequency of the double-planetary stirring kettle is 25Hz, the rotation frequency is 15Hz, and the time is 20min.
(4) And adding 30wt.% of water into the second slurry, and mixing to obtain a third slurry, wherein the revolution frequency of the double-planetary stirring kettle is 25Hz, the rotation frequency is 25Hz, and the time is 10min.
(5) Raising the stirring frequency to 40Hz, opening vacuum to less than or equal to-0.08 MPa, stirring the third slurry for 60min, adding 20wt.% of water and SBR, stirring (revolution frequency of the double-planetary stirring kettle is 40Hz, rotation frequency is 15Hz, time is 40min, and the solid content of the slurry is 50 percent), reducing revolution frequency of the double-planetary stirring kettle to 10Hz, rotation frequency is 0, vacuumizing and stirring for 45min, and removing gas in the slurry to obtain negative electrode slurry 6#.
Coating, drying, rolling and die cutting the negative electrode slurry 1# to the negative electrode slurry 6# on copper foil to prepare negative electrode sheets 1# to 6#. The negative electrode sheets 1# to 6# were used as negative electrode sheets, the metallic lithium sheet was used as a counter electrode, and 1mol/L LiPF was used 6 And mixing three components of mixed solvents according to the ratio of EC to DMC, wherein emc=1:1:1 (v/v/v) to form electrolyte, and adopting a polypropylene microporous membrane as a diaphragm to assemble the CR2032 button cells 1# to 6# in a glove box filled with inert gas.
Electrochemical performance tests were performed on CR2032 type button cells 1# through 6# and were performed on the LANHE battery test system of blue electronics inc, the corresponding electrochemical performance test results are shown in table 1. Under normal temperature conditions, the constant current of 0.1C is used for discharging to reach the voltage of 0.01V, then the constant current of 0.02C is used for discharging to reach the voltage of 0.005V, the constant current of 0.1C is used for charging to reach the voltage of 1.5V, the capacity of charging to reach 1.5V is the first charge capacity, the ratio of the first charge capacity to the first discharge capacity is the first coulomb efficiency, and the capacity retention rate is calculated after 50 weeks of circulation. And after 0.1C charge and 0.2C discharge cycle for 1 week, constant current and constant voltage charge (cut-off condition is 0.01C) was performed at 3.0C, followed by 0.2C constant current discharge, and reversible capacity at 3.0C was recorded and compared with reversible capacity at 0.2C to obtain capacity retention rate of 3C/0.2C.
Table 1 electrochemical performance test results of button cells 1# to 6# of cr2032 type
As can be seen from the results in table 1, the button cells 1# to 4# use ternary layered crystalline sulfides as the negative electrode material, and the cells have higher first charge capacity and first coulombic efficiency, and better cycle and rate performance. Button cell No. 5 adopts binary sulfide MoS 2 As a negative electrode material, the capacity is low, and the material structure is unstable, so that the cycle performance is poor. Although ternary lamellar crystalline sulfide is adopted as a negative electrode material in the button cell 6#, metal elements of the button cell are K and Sb, and the interlayer spacing is not large, so that the cycle and rate performance are poor.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the present invention can be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A sulfur negative electrode material is characterized by being a layered crystalline sulfide and having [ Cu ] 2 SbS 3 ] - Two-dimensional anion layer, ethylenediamine molecule interpenetrates with [ Cu ] 2 SbS 3 ] - In the two-dimensional anionic layer.
2. The sulfur anode material according to claim 1, wherein the [ Cu 2 SbS 3 ] - The two-dimensional anion layer is ten-membered [ Cu ] 3 Sb 2 S 8 ]Ring and six-membered [ Cu ] 2 SbS 3 ]Ring [010 ]]Two single layers formed by the plane are connected with each other to form a two-dimensional structure.
3. The sulfur anode material of claim 1, wherein the chemical formula is [ C 2 N 2 H 10 ] 0.5 Cu 2 SbS 3 ·H 2 O。
4. The preparation method of the sulfur cathode material is characterized by comprising the following steps: copper powder, antimony powder, thiourea and solvent are mixed and sealed in a high-pressure container, and the mixture is heat treated for 5 to 10 days at the temperature of 140 to 180 ℃ and then cooled and washed.
5. The method for producing a sulfur negative electrode material according to claim 4, wherein a mass ratio of the copper powder, the antimony powder, the thiourea and the solvent is 1 to 1.1:1:15 to 25:100 to 150.
6. The method for producing a sulfur anode material according to claim 4, wherein the solvent comprises ethanol and/or water.
7. The negative electrode slurry is characterized in that the preparation raw materials comprise, by mass, 80-95 parts of a negative electrode material, 1-10 parts of a conductive agent, 1-10 parts of a binder and 45-65 parts of a solvent, wherein the binder at least comprises CMC, and the negative electrode material is a sulfur negative electrode material prepared by the sulfur negative electrode material according to any one of claims 1-3 or the sulfur negative electrode material prepared by the preparation method of any one of claims 4-6.
8. The anode slurry according to claim 7, wherein the conductive agent is selected from at least one of conductive carbon black, acetylene black, graphene, and carbon nanotubes, the binder further comprises SBR, and the solvent is selected from water.
9. The method for synthesizing a negative electrode slurry according to claim 7 or 8, comprising the steps of:
(1) Vacuum stirring the conductive agent, the negative electrode material and 30-70 wt.% of CMC in a double-planetary stirring kettle to obtain a mixed material;
(2) Adding a first part of the solvent into the mixed material and mixing to obtain first slurry;
(3) Adding the rest part of CMC into the first slurry, and mixing again to obtain second slurry;
(4) Adding a second part of the solvent into the second slurry, and mixing to obtain a third slurry;
(5) And after the stirring frequency is increased to stir the third slurry, adding the rest of the solvent and the binder to stir, adjusting the solid content of the slurry to 35-55%, reducing the stirring speed, vacuumizing and stirring, and discharging the gas in the slurry.
10. Use of the sulfur anode material according to any one of claims 1 to 3 or the sulfur anode material prepared by the method for preparing a sulfur anode material according to any one of claims 4 to 6 in a lithium ion battery.
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