CN115092930A - K x C y Preparation method of battery cathode material, battery cathode material and battery - Google Patents
K x C y Preparation method of battery cathode material, battery cathode material and battery Download PDFInfo
- Publication number
- CN115092930A CN115092930A CN202210724351.1A CN202210724351A CN115092930A CN 115092930 A CN115092930 A CN 115092930A CN 202210724351 A CN202210724351 A CN 202210724351A CN 115092930 A CN115092930 A CN 115092930A
- Authority
- CN
- China
- Prior art keywords
- battery
- solution
- pole piece
- potassium
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000010406 cathode material Substances 0.000 title abstract description 20
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 41
- 239000011591 potassium Substances 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 33
- 239000010439 graphite Substances 0.000 claims abstract description 33
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007773 negative electrode material Substances 0.000 claims abstract description 24
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000007614 solvation Methods 0.000 claims abstract description 4
- 239000007774 positive electrode material Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 56
- 238000003756 stirring Methods 0.000 claims description 39
- 239000003792 electrolyte Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000009830 intercalation Methods 0.000 claims description 6
- 230000002687 intercalation Effects 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000011888 foil Substances 0.000 abstract description 11
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004146 energy storage Methods 0.000 abstract description 7
- 238000006722 reduction reaction Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000002269 spontaneous effect Effects 0.000 abstract description 3
- 239000002001 electrolyte material Substances 0.000 abstract 1
- RZTDESRVPFKCBH-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 14
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 13
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- ALLIZEAXNXSFGD-UHFFFAOYSA-N 1-methyl-2-phenylbenzene Chemical group CC1=CC=CC=C1C1=CC=CC=C1 ALLIZEAXNXSFGD-UHFFFAOYSA-N 0.000 description 1
- GVEDOIATHPCYGS-UHFFFAOYSA-N 1-methyl-3-(3-methylphenyl)benzene Chemical group CC1=CC=CC(C=2C=C(C)C=CC=2)=C1 GVEDOIATHPCYGS-UHFFFAOYSA-N 0.000 description 1
- YXBIAYXZUDJVEB-UHFFFAOYSA-N 4-(3,4-dimethylphenyl)-1,2-dimethylbenzene Chemical group C1=C(C)C(C)=CC=C1C1=CC=C(C)C(C)=C1 YXBIAYXZUDJVEB-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- BHGADZKHWXCHKX-UHFFFAOYSA-N methane;potassium Chemical compound C.[K] BHGADZKHWXCHKX-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- KVFIZLDWRFTUEM-UHFFFAOYSA-N potassium;bis(trifluoromethylsulfonyl)azanide Chemical group [K+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F KVFIZLDWRFTUEM-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/935—Carbides of alkali metals, strontium, barium or magnesium
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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 relates to a K x C y A preparation method of a battery cathode material, the battery cathode material and a battery belong to the technical field of energy storage, and solve the problems that a metal potassium foil in an existing potassium ion battery cannot be prepared in a large size and an industrial large scale, the preparation process is low in safety, and the cost is high. In the invention, biphenyl analogue is mixed with weak solvation solution to form potassium ion carrying liquid, so that the potassium ions can generate spontaneous reduction reaction and are pre-embedded into a graphite pole piece to form K x C y Pole piece to obtain K x C y A battery negative electrode material, and the use of the same x C y Battery negative electrode material, electrolyte and positive electrode material constitute battery. The method of the invention can prepare large-size K x C y The battery cathode material has the advantages of simple preparation process, short period, low cost and high safety, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of energy storage materials, in particular to a K x C y Preparation method of battery cathode material and battery cathodeMaterials and batteries.
Background
The ever-increasing energy demand and depletion of fossil fuel resources requires us to seek alternatives to sustainable energy sources, including the development of renewable energy feedstocks and sustainable energy storage technologies. At present, lithium ion batteries are undoubtedly known energy storage devices with excellent performance, but the lithium resources are deficient globally, unevenly distributed and expensive, which all limit the further application of the lithium ion batteries. Therefore, low-cost and high-performance energy storage batteries are the inevitable direction for the development of new-generation energy storage systems, and during the period, potassium ion batteries are produced.
However, for the battery using the metal potassium foil as the negative electrode, the preparation of large size cannot be realized due to the soft texture of the metal potassium, which seriously hinders the progress of industrial mass production of the potassium ion battery. In addition, the method of pouring 3D body with molten alkali metal, which is commonly used in the prior art, has a safety risk of high temperature processing, and also causes a serious heat loss during the manufacturing process, thereby increasing the cost. In addition, the use of potassium ions as a battery raw material has been receiving wide attention, for example: chinese patent applications CN109686924A and CN114300663A disclose designs based on metal potassium as a negative electrode raw material of secondary batteries, respectively. However, the design and operation process is complex, and the processing cost is high.
Disclosure of Invention
In view of the above analysis, the embodiments of the present invention are directed to providing a K x C y The battery cathode material preparation method, the battery cathode material and the battery are used for solving the problems that the metal potassium foil in the existing potassium ion battery cannot be prepared in large size and industrialized mass, the safety of the preparation process is low, and the cost is high, and can replace the application of the potassium metal foil in the basic and practical research of the potassium ion battery.
The invention provides a K x C y The preparation method of the battery negative electrode material comprises the following steps:
step 1, weighing biphenyl analogues; measuring a weak solvation solution;
step 2, putting the biphenyl analogue into a weak solvating solution, stirring until the biphenyl analogue is dissolved, and preparing a mixed solution;
step 3, weighing metal potassium, adding the metal potassium into the mixed solution obtained in the step 2, and stirring until the metal potassium is dissolved to obtain a pre-embedding solution;
step 4, preparing a graphite pole piece; putting the graphite pole piece into a container, adding the pre-embedding solution in the step (3) into the container until the liquid level is over the graphite pole piece, standing for pre-embedding, pre-embedding potassium ions in the pre-embedding solution into the graphite pole piece to form K x C y Pole pieces;
step 5, taking out the K pre-embedded in the step 4 x C y Pole piece, pre-embedded K with cleaning liquid x C y Cleaning the pole piece to remove residues on the K x C y Pre-embedding solution on the pole piece, then standing for K x C y The weak solvating solution on the pole piece is completely volatilized to obtain dry K X C Y A battery negative electrode material.
Preferably, in the step 2, the stirring speed of the biphenyl analogue dissolved in the weak solvation solution is 300-800r/min, and the stirring time is 5-10 min.
Preferably, in the step 2, a mixed solution having a biphenyl analog concentration of 0.3 to 1.1mol/L is prepared.
Preferably, in the step 3, the prepared pre-intercalation solution has a potassium concentration of 0.1-1mol/L and a biphenyl analogue concentration of 0.3-1.1 mol/L.
Preferably, the mass of the metal potassium is 0.5-30 times of that of the graphite pole piece.
Preferably, in the step 4, the standing time is 1-60 min.
On the other hand, the invention also provides K x C y The battery negative electrode material is obtained by the preparation method.
In a third aspect, the invention also provides a K x C y Battery comprising the aforementioned K X C Y A battery negative electrode material.
Preferably, the electrolyte and the positive electrode material are also included.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
(1) the method of the invention can prepare large-size K x C y The battery negative electrode material can replace metal potassium foil as a potassium metal battery negative electrode.
(2) The potassium metal in the method of the invention spontaneously carries out reduction reaction, and the potassium ions of the potassium metal can be rapidly, uniformly and proportionally embedded into the graphite pole piece to form K x C y A battery negative electrode material.
(3) The components of the mixed solution adopted by the method can not be embedded into the graphite pole piece together, and the obtained K is subjected to x C y The performance of the battery cathode material is not influenced, the operation is simple, the period is short, the cost is low, the safety is high, and the method is suitable for large-scale industrial production
(4) K prepared by the method of the invention x C y The battery cathode material has high specific capacity, good cycle performance and good rate capability.
Drawings
FIG. 1 shows KC of the present invention 8 Scanning electron microscopy of the negative electrode material;
FIG. 2 shows different Ks obtained by performing different standing times in the pre-embedding stage of the present invention x C y A first-turn charge capacity map of the battery negative electrode material;
FIG. 3 shows KC of the present invention 8 A cycle capacity-coulombic efficiency chart of a full battery consisting of a battery cathode material and PTCDA at 50 mA/g;
fig. 4 is a cycle capacity-coulombic efficiency graph of a full cell composed of a potassium metal battery anode material and PTCDA at 50mA/g in the prior art.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
In one aspect, the invention provides a K x C y Preparation method of battery cathode material capable of preparing large-size K x C y A battery anode material comprising the steps of:
step 1, weighing biphenyl analogues; measuring a weak solvating solvent; preferably, the biphenyl analogue is biphenyl or 2-methylbiphenyl or 3,3 '-dimethylbiphenyl or 4,4' -dimethylbiphenyl or 3,3',4,4' -tetramethylbiphenyl; the weak solvating solution is glycol dimethyl ether or tetrahydrofuran or 2-methyl tetrahydrofuran or tetrahydropyran solution;
and 2, putting the biphenyl analogue into a weak solvating solution, stirring until the biphenyl analogue is dissolved, and preparing a mixed solution.
And 3, weighing the metal potassium, removing an oxide layer on the surface of the metal potassium, adding the metal potassium into the mixed solution obtained in the step 2, and stirring until the metal potassium is dissolved to obtain a pre-embedded solution.
Step 4, preparing a graphite pole piece; putting the graphite pole piece into a container, adding the pre-embedding solution in the step (3) into the container until the liquid level is over the graphite pole piece, standing, pre-embedding, wherein the potassium ions in the pre-embedding solution undergo spontaneous reduction reaction to pre-embed into the graphite pole piece to form K x C y A pole piece (namely a potassium-carbon pole piece with the ratio of potassium ions to carbon atoms of X: Y).
Step 5, taking out the K pre-embedded in the step 4 x C y Pole piece, pre-embedded K with cleaning liquid x C y Cleaning the pole piece to remove residues on the K x C y Pre-embedding solution on the pole piece, then standing for K x C y The 2-methyltetrahydrofuran solution on the pole piece is completely volatilized to obtain dry K X C Y A battery negative electrode material.
Optionally, in the above step 1, the biphenyl analog is ground to 5000-; and removing water from the weak solvating solvent to obtain a weak solvating solution.
Optionally, the stirring speed of the biphenyl analogue powder dissolved in the weak solvating solution in the step 2 is 300-800r/min, and the stirring time is 5-10min, so as to prevent the weak solvating solution from volatilizing, thereby reducing the solubility of the biphenyl analogue powder; further, the stirring speed was 500r/min, the stirring time was 10min, and the stirring was performed at 102.325KP at 25 deg.C, to further prevent the volatilization of the weakly solvated solution. Sealing and stirring while stirring.
Optionally, in the mixed solution in the step 2, the concentration of the biphenyl analogues is configured to be 0.3-1.1 mol/L.
Optionally, in the step 3, the stirring speed for dissolving the metal potassium in the mixed solution in the step 2 is 300-600r/min, and the stirring time is 1-2 h; therefore, the stirring time is short, the weak solvating solution is not easy to volatilize, the metal potassium can be completely dissolved in the mixed solution, and finally the pre-embedding solution is prepared to have the potassium concentration of 0.1-1mol/L and the biphenyl analogue concentration of 0.3-1.1 mol/L.
Optionally, in the step 4, the ratio of the graphite to the conductive agent to the binder in the graphite electrode sheet is 85:5:10, wherein the conductive agent is super P, and the binder is CMC; the mass of the metal potassium is 0.5-30 times of that of the graphite, and preferably 3.83 times; the container is a glass container; placing the graphite-containing surface of the graphite pole piece in a container; the liquid level is 1-3mm over the graphite pole piece; standing for 1-60min, preferably 15min or 20 min; if the standing time is too short, the graphite pole piece cannot be pre-embedded to the state with the highest potassium capacity, and if the standing time is too long, the graphite pole piece falls off or splits.
Optionally, in the step 4, a 2-methyltetrahydrofuran solution is selected for washing; the cleaning times are 2-5 times; the standing time is 2-6 minutes.
Preferably, the concentration ratio of the biphenyl analogue to the potassium is 3:5, the mass of the graphite pole piece is 3.83 times of that of the metal potassium, the standing time of the step 4 is 15min, and the ratio of potassium ions to carbon atoms is 1:8, namely: KC 8 The pole piece has high reaction power speed and high potassium ion content. Referring to FIG. 1, KC is shown 8 Electron microscopy of the battery negative electrode material.
By adopting the preparation method, the mixed solution has a reduction potential lower than 0.2V, so that the potassium metal undergoes a spontaneous reduction reaction, and potassium ions of the potassium metal can be rapidly, uniformly and proportionally embedded into the graphite pole piece to form K x C y Pole pieces, in addition, 2-methyltetrahydrofuran and 4,4' -dimethylbiphenyl were not co-intercalated into the graphite pole pieces for the obtained K x C y The performance of the pole piece is not affected, the operation is simple, and the period is shortThe method has the advantages of low cost, high safety and suitability for large-scale industrial production, and the prepared KxCy pole piece has high specific capacity, good cycle performance and good rate performance.
On the other hand, the invention also provides K X C Y Battery cathode material prepared by the preparation method and capable of obtaining large-size K x C y A battery negative electrode material. Wherein the ratio of potassium ions to carbon atoms is changed by the mass ratio of metal potassium to graphite, the concentration of the pre-intercalation solution and the standing time, and KC is respectively obtained 48 、KC 36 、KC 24 、KC 8 Proportional battery negative electrode materials, see FIG. 2, showing K obtained at different standing times in the pre-intercalation stage under the same concentration ratio of 4,4' -dimethylbiphenyl to potassium and preparation conditions x C y The charge capacity of the first circle of the pole piece.
In a third aspect, the invention also provides K X C Y The battery comprises a positive electrode, a diaphragm, electrolyte, a negative electrode, a gasket, an elastic sheet and a battery shell, and can obtain large-size K x C y A battery; wherein, the positive electrode adopts PTCDA (namely 3,4,9, 10-perylenetetracarboxylic dianhydride) material; the diaphragm is made of glass fiber; the negative electrode adopts the above K X C Y A battery negative electrode material; electrolyte salt in the electrolyte is selected from KTFSI, KFSI and KCF 3 SO 3 、KPF 6 、KClO 4 、KNO 3 And KBF 4 At least one of; the organic solvent in the electrolyte is selected from at least one of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, 1,3 dioxolane, dioxane, tetrahydrofuran, 2 methyl tetrahydrofuran, fluoroethylene carbonate, propylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate and vinylene carbonate, and preferably, the electrolyte is a solution of ethylene glycol dimethyl ether (DME) with 3mol of potassium bis-fluorosulfonylimide (KFSI); the battery case is a button battery case with the battery case model CR 2032; during processing, the materials are assembled into a battery under the environment of 0.01PPM of argon. K of the invention X C Y The battery cathode material is applied to the secondary battery, is green and environment-friendly, has rich reserves and low cost, can realize the construction of a novel energy storage material, has simple method, high yield and good reproducibility, is easy for large-scale production, and has wide application prospect and market.
Example 1
According to the preparation method, 0.1093g of 4,4' -dimethylbiphenyl is added into 2ml of 2-methyltetrahydrofuran solution, the stirring speed is 500r/min, the stirring time is 10min, and stirring is carried out at 102.325KP and at 25 ℃ during stirring to obtain mixed solution; 0.0391g of metal potassium is added into the solution, the stirring speed is 500r/min, and the solution is stirred for 1h until the metal potassium is dissolved to obtain a pre-embedded solution. Soaking graphite electrode piece with diameter of 14mm and weight of 10.2mg in the pre-intercalation solution, standing for 15min, cleaning with 2-methyltetrahydrofuran solution, and drying to obtain KC 8 A battery negative electrode material. Mixing metal potassium foil, glass fiber diaphragm, electrolyte and KC 8 The battery cathode material, the gasket and the elastic sheet are assembled in the CR2032 button battery case in sequence and hydraulically sealed to obtain the K-KC 8 A foil half cell. The addition amount of the electrolyte is 120 mu L per battery, a charge-discharge test is carried out under the condition of current density of 27.9mAh/g at room temperature, the charge cut-off voltage is 2V, the charge capacity of the first circle is 235mAh/g, wherein the current density and the discharge capacity are calculated based on the total active mass of the positive electrode and the negative electrode.
Example 2
According to the preparation method, 0.1093g of 4,4' -dimethylbiphenyl is added into 2ml of 2-methyltetrahydrofuran solution, the stirring speed is 500r/min, the stirring time is 10min, and stirring is carried out at 102.325KP and at 25 ℃ during stirring to obtain mixed solution; 0.0391g of metal potassium is added into the solution, the stirring speed is 500r/min, and the solution is stirred for 1h until the metal potassium is dissolved to obtain a pre-embedded solution. Soaking graphite electrode piece with diameter of 14mm and weight of 10.2mg in the pre-intercalation solution, standing for 15min, cleaning with 2-methyltetrahydrofuran, and drying to obtain KC 8 A battery negative electrode material. Mixing PTCDA, glass fiber diaphragm, electrolyte and KC 8 Battery cathodeThe material, the gasket and the elastic sheet are assembled in the CR2032 button battery case in sequence and are sealed hydraulically to obtain the PTCDA-KC 8 And (4) full cell. Referring to fig. 3, the addition amount of the electrolyte is 120 μ L per cell, a charge and discharge test is performed at room temperature under a current density of 50mAh/g, the charge cut-off voltage is 3.4V, the first-cycle discharge capacity is 134mAh/g (calculated based on the active mass of the positive electrode), and the capacity retention rate is 80.5% after 60 cycles.
Comparative example 1
According to the preparation method, 0.3644g of 4,4' -dimethylbiphenyl is added into 2ml of 2-methyltetrahydrofuran solution, the stirring speed is 500r/min, the stirring time is 10min, and stirring is carried out at 102.325KP and at 25 ℃ during stirring to obtain mixed solution; 0.0391g of metal potassium is added into the solution, the stirring speed is 500r/min, and the solution is stirred for 1h until the metal potassium is dissolved to obtain a pre-embedded solution. Soaking a graphite pole piece with the diameter of 14mm and the weight of 10.2mg in the pre-embedding solution, standing for 15min, cleaning with 2-methyltetrahydrofuran, and drying to obtain KC 48 A battery negative electrode material. Mixing metal potassium foil, glass fiber diaphragm, electrolyte and KC 48 The battery cathode material, the gasket and the elastic sheet are assembled in the CR2032 button battery case in sequence and hydraulically sealed to obtain the K-KC 48 A foil half cell. The addition amount of the electrolyte is 120 mu L per battery, a charge-discharge test is carried out under the condition of current density of 27.9mAh/g at room temperature, the charge cut-off voltage is 2V, and the charge capacity of the first circle is only 25 mAh/g.
Comparative example 2
According to the preparation method, 0.1093g of 4,4' -dimethylbiphenyl is added into 2ml of 2-methyltetrahydrofuran solution, the stirring speed is 500r/min, the stirring time is 10min, and the stirring is carried out at 102.325KP and 25 ℃ to obtain a mixed solution; 0.0391g of metal potassium is added into the solution, the stirring speed is 500r/min, and the solution is stirred for 1h until the metal potassium is dissolved to obtain a pre-embedded solution. And soaking a graphite pole piece with the diameter of 14mm and the weight of 10.2mg into the pre-embedding solution, standing for 1min, and then washing and drying by using 2-methyltetrahydrofuran to finally obtain the battery negative electrode material in a coexisting state. Mixing metal potassium foil, glass fiber diaphragm, electrolyte and K 1 C 36 -K 1 C 24 -K 1 C 8 The battery cathode material, the gasket and the elastic sheet are assembled in the CR2032 button battery case in sequence and are sealed hydraulically to obtain K-K 1 C 36 -K 1 C 24 -K 1 C 8 A foil half cell. The addition amount of the electrolyte is 120 mu L per battery, a charge-discharge test is carried out under the condition of current density of 27.9mAh/g at room temperature, the charge cut-off voltage is 2V, and the charge capacity of the first circle is only 89 mAh/g.
Comparative example 3
And assembling the PTCDA, the glass fiber diaphragm, the electrolyte, the K metal negative electrode material, the gasket and the elastic sheet in the CR2032 button battery case in sequence, and hydraulically sealing to obtain the PTCDA-K metal full battery. Referring to fig. 4, the addition amount of the electrolyte is 120 μ L per cell, a charge and discharge test is performed at room temperature under a current density of 50mAh/g, the charge cut-off voltage is 3.4V, the first-cycle discharge capacity is 131.5mAh/g (calculated based on the active mass of the positive electrode), and the capacity retention rate is 78% after 60 cycles.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (9)
1. K x C y The preparation method of the battery negative electrode material is characterized by comprising the following steps:
step 1, weighing biphenyl analogues; measuring a weak solvation solution;
step 2, putting the biphenyl analogue into a weak solvating solution, stirring until the biphenyl analogue is dissolved, and preparing a mixed solution;
step 3, weighing metal potassium, adding the metal potassium into the mixed solution obtained in the step 2, and stirring until the metal potassium is dissolved to obtain a pre-embedding solution;
step 4, preparing a graphite pole piece; putting the graphite pole piece into a container, adding the pre-embedding solution in the step (3) into the container until the liquid level is over the graphite pole piece, and then standing the containerPre-embedding, pre-embedding potassium ions in the pre-embedding solution into the graphite pole piece to form K x C y Pole pieces;
step 5, taking out the K pre-embedded in the step 4 x C y Pole piece, pre-embedded K with cleaning liquid x C y Cleaning the pole piece to remove residues on the K x C y Pre-embedding solution on the pole piece, then standing for K x C y The weak solvating solution on the pole piece is completely volatilized to obtain dry K X C Y A battery negative electrode material.
2. The method as set forth in claim 1, wherein in the step 2, the stirring speed for dissolving the biphenyl analog in the weak solvating solution is 300-800r/min, and the stirring time is 5-10 min.
3. The production method according to claim 1 or 2, wherein in the step 2, a mixed solution having a biphenyl analog concentration of 0.3 to 1.1mol/L is prepared.
4. The production method according to claim 1 or 2, wherein in the step 3, the prepared pre-intercalation solution has a potassium concentration of 0.1 to 1mol/L and a biphenyl analogue concentration of 0.3 to 1.1 mol/L.
5. The production method according to claim 1 or 2, wherein the mass of the metallic potassium is 0.5 to 30 times that of the graphite pole piece.
6. The production method according to claim 1 or 2, wherein in the step 4, the standing time is 1 to 60 min.
7. K x C y A battery negative electrode material characterized by being obtained by the production method according to any one of claims 1 to 6.
8. K x C y Battery, its characteristicsIn that it comprises K as claimed in claim 7 X C Y A battery negative electrode material.
9. K according to claim 8 x C y The battery is characterized by further comprising an electrolyte and a positive electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210724351.1A CN115092930A (en) | 2022-06-23 | 2022-06-23 | K x C y Preparation method of battery cathode material, battery cathode material and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210724351.1A CN115092930A (en) | 2022-06-23 | 2022-06-23 | K x C y Preparation method of battery cathode material, battery cathode material and battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115092930A true CN115092930A (en) | 2022-09-23 |
Family
ID=83292390
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210724351.1A Pending CN115092930A (en) | 2022-06-23 | 2022-06-23 | K x C y Preparation method of battery cathode material, battery cathode material and battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115092930A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08124559A (en) * | 1994-10-27 | 1996-05-17 | Sharp Corp | Manufacture of lithium secondary battery and of negative electrode active material |
| CN101118978A (en) * | 2006-08-04 | 2008-02-06 | 韩磊 | Lithium ion battery with FePO4/LixCn as electrode couple and method for making same |
| JP2011243567A (en) * | 2010-04-20 | 2011-12-01 | Jfe Chemical Corp | Negative electrode material for lithium ion secondary battery and method of manufacturing the same, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| CN104766947A (en) * | 2014-01-03 | 2015-07-08 | 中国科学院物理研究所 | Preliminary metal metallization method and its application in battery material |
| CN110729479A (en) * | 2019-10-23 | 2020-01-24 | 江苏理工学院 | Potassium ion battery and manufacturing method and application thereof |
| CN113046768A (en) * | 2021-03-15 | 2021-06-29 | 东北师范大学 | Potassium vanadyl fluorophosphate, preparation method and application thereof, and potassium ion battery |
| CN113130853A (en) * | 2021-04-19 | 2021-07-16 | 中国科学技术大学 | Modified alkali metal ion battery negative plate, preparation method and application thereof |
| CN114597077A (en) * | 2022-03-21 | 2022-06-07 | 山东大学 | Application of pre-lithiated carbon negative electrode material in sodium ion capacitor and potassium ion capacitor |
| WO2022120592A1 (en) * | 2020-12-08 | 2022-06-16 | 深圳先进技术研究院 | Preparation of negative electrode material base on potassium polycarboxylate and graphite composite and use of potassium ion battery |
-
2022
- 2022-06-23 CN CN202210724351.1A patent/CN115092930A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08124559A (en) * | 1994-10-27 | 1996-05-17 | Sharp Corp | Manufacture of lithium secondary battery and of negative electrode active material |
| CN101118978A (en) * | 2006-08-04 | 2008-02-06 | 韩磊 | Lithium ion battery with FePO4/LixCn as electrode couple and method for making same |
| JP2011243567A (en) * | 2010-04-20 | 2011-12-01 | Jfe Chemical Corp | Negative electrode material for lithium ion secondary battery and method of manufacturing the same, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| CN104766947A (en) * | 2014-01-03 | 2015-07-08 | 中国科学院物理研究所 | Preliminary metal metallization method and its application in battery material |
| CN110729479A (en) * | 2019-10-23 | 2020-01-24 | 江苏理工学院 | Potassium ion battery and manufacturing method and application thereof |
| WO2022120592A1 (en) * | 2020-12-08 | 2022-06-16 | 深圳先进技术研究院 | Preparation of negative electrode material base on potassium polycarboxylate and graphite composite and use of potassium ion battery |
| CN113046768A (en) * | 2021-03-15 | 2021-06-29 | 东北师范大学 | Potassium vanadyl fluorophosphate, preparation method and application thereof, and potassium ion battery |
| CN113130853A (en) * | 2021-04-19 | 2021-07-16 | 中国科学技术大学 | Modified alkali metal ion battery negative plate, preparation method and application thereof |
| CN114597077A (en) * | 2022-03-21 | 2022-06-07 | 山东大学 | Application of pre-lithiated carbon negative electrode material in sodium ion capacitor and potassium ion capacitor |
Non-Patent Citations (2)
| Title |
|---|
| DENG XL: "KxCy phase induced expanded interlayer in ultra-thin carbon toward full potassium-ion capacitors", CARBON ENERGY, pages 1151 - 1168 * |
| 雷宇;韩达;秦磊;翟登云;康飞宇;: "钾离子电池中碳负极材料的研究进展", 新型炭材料, no. 06 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109004199B (en) | Preparation method of biomass hard carbon material for negative electrode of sodium-ion battery | |
| CN107069094B (en) | A kind of lithium-ion battery electrolytes of ultra-low temperature discharge | |
| CN109167035A (en) | Carbon-coated ferrous sulfide negative electrode material, preparation method and its sodium-ion battery of preparation | |
| CN105576220B (en) | A kind of preparation method of cellular carbon-coated LiFePO 4 for lithium ion batteries positive electrode | |
| CN103872330A (en) | Lithium ion battery negative electrode material and preparation method thereof | |
| CN106629665B (en) | Molten-salt growth method prepares sulfur doping hard carbon nanometer sheet and its application in sodium-ion battery | |
| CN108832122A (en) | Improve the method for electrochemical performances of lithium iron phosphate using copper/graphene | |
| CN108777294A (en) | A kind of porous spherical MoN that the carbon being made of nanometer sheet is supported and its application as negative material in lithium battery | |
| CN107623109A (en) | A kind of preparation method of high power capacity long circulating stability lithium ion battery negative material | |
| CN108306001B (en) | Lithium ion battery cathode material Fe3O4Preparation method of/N-C | |
| CN110752360B (en) | S-Ni3Preparation method of C/NiO composite lithium-sulfur battery positive electrode material | |
| CN109216684A (en) | A kind of flower-shaped FeSxThe preparation method and purposes of/C nano composite material | |
| CN109467080B (en) | Preparation method and application of graphitized hollow carbon microspheres for sulfur loading | |
| CN110233251A (en) | A kind of preparation method and applications of porous silicon/carbon composite material | |
| CN113871605A (en) | Pre-lithiated silicon-based negative electrode material and preparation method and application thereof | |
| CN100527482C (en) | Making method for LiFePO4-carbon composite cathode material of lithium ion battery | |
| CN111477977B (en) | Water-ether mixed electrolyte for lithium ion battery and preparation method thereof | |
| CN102070199B (en) | Method for preparing micron frame-shaped manganese series lithium ion battery cathode material | |
| CN109360947B (en) | Preparation method of porous carbon cathode material of quasi-solid-state lithium-sulfur battery | |
| CN111224166A (en) | Ether electrolyte, preparation method and application thereof | |
| CN114464806B (en) | Organic positive electrode material of sodium ion battery with stable circulation and reversible sodium removal and preparation method thereof | |
| CN115092930A (en) | K x C y Preparation method of battery cathode material, battery cathode material and battery | |
| CN105609771A (en) | Nitrogen-doped multi-porous carbon negative electrode material and preparation method and application thereof | |
| CN101478062A (en) | Composite electrolytic solution for lithium ionic battery, preparation and use thereof | |
| CN112436112B (en) | Nitrogen-doped siraitia grosvenorii residue-based C/SnO2Composite material, preparation and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |