CN116169429A - Preparation method of lithium-sulfur battery based on phosphorus-based anion frame polymer diaphragm coating - Google Patents
Preparation method of lithium-sulfur battery based on phosphorus-based anion frame polymer diaphragm coating Download PDFInfo
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 72
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 47
- 239000011574 phosphorus Substances 0.000 title claims abstract description 47
- 150000001450 anions Chemical class 0.000 title claims abstract description 43
- 238000000576 coating method Methods 0.000 title claims abstract description 17
- 239000011248 coating agent Substances 0.000 title claims abstract description 16
- 229920000642 polymer Polymers 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- 125000000129 anionic group Chemical group 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000010405 anode material Substances 0.000 claims abstract description 8
- 239000010406 cathode material Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 5
- 239000002178 crystalline material Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 150000003536 tetrazoles Chemical class 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000001291 vacuum drying Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- PMGUSTCDZYVHMQ-UHFFFAOYSA-N 1,2,3,4,5-pentamethyltetrazolidine Chemical compound CC1N(N(N(N1C)C)C)C PMGUSTCDZYVHMQ-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 238000005520 cutting process Methods 0.000 claims description 14
- 239000004570 mortar (masonry) Substances 0.000 claims description 14
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000004033 plastic Substances 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 12
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 238000007790 scraping Methods 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005357 flat glass Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 238000002484 cyclic voltammetry Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 229920005597 polymer membrane Polymers 0.000 claims 4
- 239000002002 slurry Substances 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 description 13
- 239000002033 PVDF binder Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910013210 LiNiMnCoO Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003446 ligand Substances 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
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- 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
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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Abstract
The invention discloses a preparation method of a lithium-sulfur battery based on a phosphorus-based anion frame polymer diaphragm coating, which comprises the steps of firstly synthesizing an anion-type organic metal frame material, and mixing the anion-type organic metal frame material with conductive carbon black (SuperP) and a binder (PV)DF) is prepared into slurry according to a certain proportion, and the slurry is coated on a commercial diaphragm to form the diaphragm of the lithium-sulfur battery of the anionic organic metal frame material. And finally, assembling the lithium-sulfur battery with a sulfur-loaded carbon nano tube composite anode material and a cathode material lithium sheet to obtain the lithium-sulfur battery with good thermal stability, small impedance and good cycle performance. The material has 1127mAh g under the rated capacitance of 0.5C ‑1 At a rated capacity of 3C, 815mAh g ‑1 The coulomb efficiency is close to 100%.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur battery materials, and particularly relates to a preparation method of a lithium-sulfur battery based on a phosphorus-based anion frame polymer diaphragm coating.
Background
The electrochemical performance of existing power cells is determined to a high extent by the theoretical gram capacity that can be provided by the materials, and the most widely used positive electrode materials of existing secondary cells include lithium manganate (LiMn) 2 O 4 ) Lithium cobalt oxide (LiCoO) 2 ) Ternary materials (LiNiMnCoO 2 ) Lithium iron phosphate (LiFePO) 4 ) And the highest theoretical capacity of the battery is not more than 190mAh/g, and the battery capacity is relatively low, so that the improvement of the energy density of the lithium battery is limited to a certain extent. Therefore, in order to increase the specific capacity of the battery, increase the energy density of the battery, reduce the manufacturing cost of the battery, improve the cycle performance of the battery and improve the safety performance of the battery, new battery materials with higher capacity have to be searched for a long time, and sulfur materials therein are widely accepted by people in the industry, and the sulfur materials are very abundant in the earth, very available, low in price and basically nontoxic, and have a hopeful of reversible reaction with the electrochemical reaction of lithium in the charge and discharge processes. Lithium sulfur batteries have therefore become a focus of attention for researchers in recent years.
Lithium sulfur batteries are secondary batteries, can be charged and discharged many times, and sulfur provides a high theoretical energy density (2600 Wh/kg) and a high theoretical gram capacity (1675 mAh/g), which is 8-10 times that of commercial lithium batteries, and is considered to be one of the next generation of high-energy battery systems. Although lithium sulfur batteries have such high energy density and theoretical capacity, the cycle performance of lithium sulfur batteries is found to be poor during experiments, so researchers have made many modifications on positive and negative electrode materials, and the fields of various research materials have contributed to their respective strengths.
In recent years, a separator layer is gradually discovered as an important influencing factor in the process of ion conduction between two electrodes, so that a great deal of research is conducted on the aspect of modifying a lithium sulfur battery separator. For example, a porous material is used to increase the conductive agent and enhance the ion transmission function of the membrane. The composite sulfur (S) positive electrode in the lithium sulfur battery is used as a positive electrode material of the lithium sulfur battery, the metal lithium sheet is used as a negative electrode material of the lithium sulfur battery, the positive electrode and the negative electrode are required to be separated by a diaphragm, the diaphragms commonly used in the prior art are made of PP, PE and the like, the typical PP diaphragms are made of cellgard 2400, cellgard 2500 and the like, the diaphragms are single-layer diaphragms, the porosity is different, the efficiency of lithium ion migration is influenced by the porosity difference, the commercial diaphragm is made of a polymer material, the conductivity is poor, and the problem of short circuit and poor stability of the battery is easily caused by the penetration of lithium dendrites, so that further research is required in the modification of the diaphragms.
Disclosure of Invention
The invention aims to provide a preparation method of a lithium-sulfur battery based on a phosphorus-based anion frame polymer diaphragm, which solves the problems of poor conductivity and poor thermal stability of the conventional lithium-sulfur battery diaphragm.
The technical scheme adopted by the invention is that the preparation method of the lithium sulfur battery based on the phosphorus-based anion frame polymer diaphragm comprises the following specific operation steps:
step 1: sequentially weighing zinc nitrate hexahydrate solid and pentamethyltetrazole powder, adding the zinc nitrate hexahydrate solid and pentamethyltetrazole powder into a polytetrafluoroethylene reaction kettle containing N, N-dimethylformamide solution, continuously adding phosphorous acid solution, stirring at room temperature until the solution is uniform and transparent, placing the solution into the reaction kettle to react for 3 days at 85 ℃, then washing the solution with methanol for at least three times, and centrifugally drying to obtain a phosphorus-based anion frame-type metal tetrazole crystalline material A;
step 2: mixing the phosphorus-based anion frame-type metal tetrazole crystalline material A obtained in the step 1, conductive carbon black and a binder in an agate mortar for forceful grinding, and continuously adding N-methyl pyrrolidone into the mortar until uniform slightly sticky black paste B is formed;
step 3: cutting a diaphragm, fixing the diaphragm on a clean and flat glass plate sterilized by alcohol, scraping the black paste B obtained in the step 2 on the surface of the diaphragm by a film scraper, transferring the obtained modified diaphragm and the glass plate into a vacuum drying oven, and drying to obtain a uniform modified diaphragm C;
step 4: taking out the modified diaphragm C obtained in the step 3, and cutting the diaphragm C into a wafer by a tablet press to obtain a modified battery diaphragm D;
step 5: the modified battery diaphragm D obtained in the step 4 is separately filled into a plastic package bag, and is placed into a vacuum drying oven to obtain a phosphorus-based anion type organic metal frame material lithium sulfur battery diaphragm E;
step 6: and (3) assembling the battery diaphragm E obtained in the step (5) with a sulfur-loaded carbon nano tube composite anode material and a sulfur-loaded carbon nano tube composite cathode material lithium sheet into a lithium sulfur battery, and testing the rate capability, impedance and CV under different currents.
The present invention is also characterized in that,
in the step 1, the mass ratio of the zinc nitrate hexahydrate solid to the pentamethyltetrazole powder is 12:5, and the volume ratio of the phosphorous acid solution to the solvent N, N-dimethylformamide solution is 100:3.
The zinc nitrate hexahydrate solid in the step 1 can be replaced by any one of zinc chloride and zinc acetate.
In the step 2, the mass ratio of the anionic frame type metal tetrazole crystalline material A to the conductive carbon black to the binder is 8:1:1, and the grinding time is at least 30min.
The vacuum drying temperature in the step 3 is 60-70 ℃ and the drying time is not less than 12h.
The diameter of the cut pieces in step 4 is 16mm.
The vacuum drying temperature in the step 5 is 60-70 ℃ and the drying time is 8-12 h.
And 6, assembling a lithium-sulfur battery to test electrochemical performance: the multiplying power performance is tested under different currents, the currents are set to be 0.5C, 1C, 2C, 3C and 5C, the parameter frequency of the test when the Electrochemical Impedance (EIS) is tested is 0.01-1000000Hz, the cyclic voltammetry test voltage is 1.7V-2.7V, and the scanning rate is 0.001V/s.
The membrane model in the step 3 is celgard2400 membrane.
The key steps in the invention are synthesized by the following principle:
synthesis of (one) phosphorus-based anion frame-type metal tetrazole crystalline material: the negative ion frame type metal tetrazole crystalline material powder A is characterized in that phosphorous acid is used for introducing negative charge in the synthesis process, so that the prepared metal tetrazole crystalline material is negatively charged, and the negative charge material is used for a lithium sulfur battery diaphragm layer, thereby being beneficial to adsorbing Li through electrostatic action + Improve Li + The migration number between the anode and the cathode is increased, so that the electrochemical performance of the lithium-sulfur battery is improved.
(II) preparation of a pretreatment phosphorus-based anion frame polymer battery lithium sulfur diaphragm coating: the celgard2400 membrane is selected as the substrate of the lithium sulfur battery membrane, on one hand, the membrane modification material can be uniformly adhered to the surface due to the porosity of the membrane, and on the other hand, compared with other PP type membranes, the celgard2400 membrane is beneficial to processing and has high cost performance.
The preparation method of the lithium-sulfur battery diaphragm based on the phosphorus-based anion frame material comprises the following steps: from zinc nitrate hexahydrate [ Zn (NO 3) 2 ·6(H 2 O)]The anionic frame type metal tetrazole crystalline material A synthesized by the solid and the pentamethyltetrazole (5-MTZ) powder has good thermal stability, a large number of mesopores and micropores exist, the solid and the pentamethyltetrazole (5-MTZ) powder have ultrahigh specific surface area, the lithium ion is favorably and rapidly transported, the cycle characteristic of a lithium-sulfur battery is improved, the slurry prepared by the solid and the pentamethyltetrazole (5-MTZ) powder is scraped on the surface of a celgard2400 diaphragm, and the modified diaphragm has better characteristic.
The preparation method of the lithium sulfur battery based on the phosphorus-based anion frame polymer diaphragm adopts a knife coating method to scrape an anion frame type diaphragm coating on a celgard2400 diaphragm, and 1127 mAh.g is arranged under the current density of 0.5C -1 First capacity, and has a rate capability of up to 5C.
The beneficial effects of the invention are as follows:
(1) Four nitrogen in ligand pentamethyltetrazole in phosphorus-based anion frame type metal tetrazole crystalline material A prepared by a hydrothermal method can have strong coordination effect with metal zinc, so that crystalline material with good thermal stability is obtained, and the highly crystalline negative frame is favorable for lithium ion conduction.
(2) The slurry prepared from the phosphorus-based anion frame-type metal tetrazole crystalline material is coated on the surface of the cellgard 2400 diaphragm by a blade coating method, so that the anion-type organic metal frame-type lithium sulfur battery diaphragm is constructed, and the diaphragm is prepared by a simple method, and combines the advantages of the two materials. The method is simple and easy to implement, is not only suitable for the membrane of the general celgard2400, but also can be used for modifying other battery membranes, and the butcher material of the composite membrane not only can be used for modifying lithium sulfur batteries, but also can be used for modifying membranes of other solid batteries, and has wide application range.
Drawings
FIG. 1 is a flow chart of a method for preparing a lithium sulfur battery based on a phosphorus-based anionic frame polymer separator according to the present invention;
FIG. 2 is an X-ray diffraction pattern of a phosphor-based anionic frame crystal material of the present invention;
fig. 3 is a lithium sulfur battery (PO) of the invention 3 -LSBs) current density versus potential plot (CV);
fig. 4 is an Electrochemical Impedance (EIS) of a lithium sulfur battery of the present invention.
Fig. 5 is a graph of the rate performance of a lithium sulfur battery of the present invention at different currents.
Fig. 6 is a graph of efficiency versus specific capacity for a lithium sulfur battery of the present invention after 300 cycles at rated capacity 3C.
Detailed Description
The preparation method of the lithium sulfur battery based on the phosphorus-based anion frame polymer diaphragm comprises the steps of synthesizing a phosphorus-based anion frame material, blending the phosphorus-based anion frame material with conductive carbon black (SuperP) and a binder PVDF, preparing slurry, scraping and coating the slurry on a celgard2400 diaphragm to obtain a modified diaphragm, and assembling the modified diaphragm with a sulfur anode and a lithium cathode into the lithium sulfur battery.
The invention will be further illustrated with reference to specific examples.
Example 1:
the preparation method of the lithium sulfur battery based on the phosphorus-based anion frame polymer diaphragm has the following specific operation steps as shown in a figure 1:
step 1: sequentially weighing zinc nitrate hexahydrate [ Zn (NO) 3 ) 2 ·6(H 2 O)]Solid and pentamethyltetrazole (5-MTZ) powder (mass ratio 12:5) were added to a polytetrafluoroethylene reaction vessel containing 5mLN, N-Dimethylformamide (DMF) solution, and 3 drops of phosphorous acid (H) 3 PO 3 ) Stirring the solution at room temperature until the solution is uniform and transparent, putting the solution into a reaction kettle for reacting for 3 days at 85 ℃, then washing with methanol for at least three times, and centrifugally drying to obtain a white anion frame-type metal tetrazole crystalline material A;
step 2: mixing the anionic frame-type metal tetrazole crystalline material A obtained in the step 1, conductive carbon black (SuperP) and a binder (PVDF) (the mass ratio is 8:1:1), and forcefully grinding for 30min in an agate mortar, and continuously adding N-methylpyrrolidone (NMP) into the mortar until a uniform slightly sticky black paste B is formed;
step 3: cutting a commercial diaphragm celgard2400, fixing the commercial diaphragm celgard2400 on a clean and flat glass plate after being sterilized by alcohol, scraping the black paste B obtained in the step 2 on the surface of the celgard2004 diaphragm by a film scraper, transferring the obtained modified diaphragm and the glass plate into a vacuum drying oven at the temperature of 60 ℃ for drying for 12 hours, and obtaining a uniform modified diaphragm C;
step 4: taking out the modified diaphragm C obtained in the step 4, and cutting the diaphragm C into a circular sheet with the diameter of 16mm by a tablet press to obtain a modified battery diaphragm D;
step 5: and (3) putting the modified battery diaphragm D obtained in the step (4) into a plastic package bag separately, and putting the plastic package bag into a vacuum drying oven at 60 ℃ for drying for 12 hours to obtain the lithium-sulfur battery diaphragm E made of the anion type organic metal frame material.
Step 6: and (3) assembling the lithium sheet of the battery diaphragm E and S@CNT composite anode material and the lithium sheet of the cathode material obtained in the step (5) into a lithium sulfur battery, and testing the rate performance (0.5C, 1C, 2C, 3C and 5C currents), the impedance (the frequency is 0.01-1000000 Hz) and the CV (1.7V-2.7V) under different currents, wherein the scanning rate is 0.001V/s.
Example 2:
step 1: sequentially weighing zinc chloride (ZnCl) 2 ) Solid and pentamethyltetrazole (5-MTZ) powder (mass ratio 12:5) were added to a polytetrafluoroethylene reaction vessel containing 5mLN, N-Dimethylformamide (DMF) solution, and 3 drops of phosphorous acid (H) 3 PO 3 ) Stirring the solution at room temperature until the solution is uniform and transparent, putting the solution into a reaction kettle for reacting for 3 days at 85 ℃, then washing with methanol for at least three times, and centrifugally drying to obtain a white phosphorus-based anion frame-type metal tetrazole crystalline material A;
step 2: mixing the phosphorus-based anion frame-type metal tetrazole crystalline material A obtained in the step 1, conductive carbon black (SuperP) and a binder (PVDF) (the mass ratio is 8:1:1), and forcefully grinding for 30min in an agate mortar, and continuously adding N-methylpyrrolidone (NMP) into the mortar until a uniform slightly sticky black paste B is formed;
step 3: cutting a commercial diaphragm celgard2400, fixing the commercial diaphragm celgard2400 on a clean and flat glass plate after being sterilized by alcohol, scraping the black paste B obtained in the step 2 on the surface of the celgard2004 diaphragm by a film scraper, transferring the obtained modified diaphragm and the glass plate into a vacuum drying oven at the temperature of 60 ℃ for drying for 12 hours, and obtaining a uniform modified diaphragm C;
step 4: taking out the modified diaphragm C obtained in the step 4, and cutting the diaphragm C into a circular sheet with the diameter of 16mm by a tablet press to obtain a modified battery diaphragm D;
step 5: and (3) putting the modified battery diaphragm D obtained in the step (4) into a plastic package bag separately, and putting the plastic package bag into a vacuum drying oven at 60 ℃ for drying for 12 hours to obtain the phosphorus-based anion type organic metal frame material lithium sulfur battery diaphragm E.
Step 6: and (3) assembling the lithium sheet of the battery diaphragm E and S@CNT composite anode material and the lithium sheet of the cathode material obtained in the step (5) into a lithium sulfur battery, and testing the rate performance (0.5C, 1C, 2C, 3C and 5C currents), the impedance (the frequency is 0.01-1000000 Hz) and the CV (1.7V-2.7V) under different currents, wherein the scanning rate is 0.001V/s.
Example 3:
step 1: sequentially weighing zinc nitrate hexahydrate [ Zn (NO) 3 ) 2 ·6(H 2 O)]Solid and pentamethyltetrazole (5-MTZ) powder (mass ratio 2:1) were added to a polytetrafluoroethylene reaction vessel containing 5mLN, N-Dimethylformamide (DMF) solution, and 3 drops of phosphorous acid (H) 3 PO 3 ) Stirring the solution at room temperature until the solution is uniform and transparent, putting the solution into a reaction kettle for reacting for 3 days at 85 ℃, then washing with methanol for at least three times, and centrifugally drying to obtain a phosphorus-based white anion frame-type metal tetrazole crystalline material A;
step 2: mixing the phosphorus-based anion frame-type metal tetrazole crystalline material A obtained in the step 1, conductive carbon black (SuperP) and a binder (PVDF) (the mass ratio is 8:1:1), forcibly grinding the mixture in an agate mortar for not less than 30min, and continuously adding N-methylpyrrolidone (NMP) into the mortar until uniform slightly sticky black paste B is formed;
step 3: cutting a commercial diaphragm celgard2400, fixing the commercial diaphragm celgard2400 on a clean and flat glass plate after being sterilized by alcohol, scraping the black paste B obtained in the step 2 on the surface of the celgard2004 diaphragm by a film scraper, transferring the obtained modified diaphragm and the glass plate into a vacuum drying oven at the temperature of 60 ℃ for drying for 12 hours, and obtaining a uniform modified diaphragm C;
step 4: taking out the modified diaphragm C obtained in the step 4, and cutting the diaphragm C into a circular sheet with the diameter of 16mm by a tablet press to obtain a modified battery diaphragm D;
step 5: and (3) putting the modified battery diaphragm D obtained in the step (4) into a plastic package bag separately, and putting the plastic package bag into a vacuum drying oven at 60 ℃ for drying for 12 hours to obtain the phosphorus-based anion type organic metal frame material lithium sulfur battery diaphragm E.
Step 6: and (3) assembling the lithium sheet of the battery diaphragm E and S@CNT composite anode material and the lithium sheet of the cathode material obtained in the step (5) into a lithium sulfur battery, and testing the rate performance (0.5C, 1C, 2C, 3C and 5C currents), the impedance (the frequency is 0.01-1000000 Hz) and the CV (1.7V-2.7V) under different currents, wherein the scanning rate is 0.001V/s.
Example 4:
step 1: sequentially weighing zinc nitrate hexahydrate [ Zn (NO) 3 ) 2 ·6(H 2 O)]Solid and pentamethyltetrazole (5-MTZ) powder (mass ratio 12:5) were added to a polytetrafluoroethylene reaction vessel containing 5mLN, N-Dimethylformamide (DMF) solution, and 3 drops of phosphorous acid (H) 3 PO 3 ) Stirring the solution at room temperature until the solution is uniform and transparent, putting the solution into a reaction kettle to react for 2 days at 100 ℃, then washing the solution with methanol for at least three times, and centrifugally drying the solution to obtain a white phosphorus-based anion frame-type metal tetrazole crystalline material A;
step 2: mixing the phosphorus-based anion frame-type metal tetrazole crystalline material A obtained in the step 1, conductive carbon black (SuperP) and a binder (PVDF) (mass ratio 7:2:1), forcibly grinding in an agate mortar for not less than 30min, and continuously adding N-methylpyrrolidone (NMP) into the mortar until uniform slightly sticky black paste B is formed;
step 3: cutting a commercial diaphragm celgard2400, fixing the commercial diaphragm celgard2400 on a clean and flat glass plate after being sterilized by alcohol, scraping the black paste B obtained in the step 2 on the surface of the celgard2004 diaphragm by a film scraper, transferring the obtained modified diaphragm and the glass plate into a vacuum drying oven at the temperature of 60 ℃ for drying for 12 hours, and obtaining a uniform modified diaphragm C;
step 4: taking out the modified diaphragm C obtained in the step 4, and cutting the diaphragm C into a circular sheet with the diameter of 16mm by a tablet press to obtain a modified battery diaphragm D;
step 5: and (3) putting the modified battery diaphragm D obtained in the step (4) into a plastic package bag separately, and putting the plastic package bag into a vacuum drying oven at 60 ℃ for drying for 12 hours to obtain the phosphorus-based anion type organic metal frame material lithium sulfur battery diaphragm E.
Step 6: and (3) assembling the lithium sheet of the battery diaphragm E and S@CNT composite anode material and the lithium sheet of the cathode material obtained in the step (5) into a lithium sulfur battery, and testing the rate performance (0.5C, 1C, 2C, 3C and 5C currents), the impedance (the frequency is 0.01-1000000 Hz) and the CV (1.7V-2.7V) under different currents, wherein the scanning rate is 0.001V/s.
Example 5:
step 1: sequentially weighing hexahydrateZinc nitrate [ Zn (NO) 3 ) 2 ·6(H 2 O)]Solid and pentamethyltetrazole (5-MTZ) powder (mass ratio 12:5) were added to a polytetrafluoroethylene reaction vessel containing 5mLN, N-Dimethylformamide (DMF) solution, and 3 drops of phosphorous acid (H) 3 PO 3 ) Stirring the solution at room temperature until the solution is uniform and transparent, putting the solution into a reaction kettle for reacting for 3 days at 85 ℃, then washing with methanol for at least three times, and centrifugally drying to obtain a phosphorus-based white anion frame-type metal tetrazole crystalline material A;
step 2: mixing the phosphorus-based anion frame-type metal tetrazole crystalline material A obtained in the step 1, conductive carbon black (SuperP) and a binder (PVDF) (the mass ratio is 8:1:1), and forcefully grinding for 40min in an agate mortar, and continuously adding N-methylpyrrolidone (NMP) into the mortar until a uniform slightly sticky black paste B is formed;
step 3: cutting a commercial diaphragm celgard2400, fixing the commercial diaphragm celgard2400 on a clean and flat glass plate after being sterilized by alcohol, scraping the black paste B obtained in the step 2 on the surface of the celgard2004 diaphragm by a film scraper, transferring the obtained modified diaphragm and the glass plate into a vacuum drying oven at the temperature of 70 ℃ for drying for 8 hours, and obtaining a uniform modified diaphragm C;
step 4: taking out the modified diaphragm C obtained in the step 4, and cutting the diaphragm C into a circular sheet with the diameter of 16mm by a tablet press to obtain a modified battery diaphragm D;
step 5: and (3) putting the modified battery diaphragm D obtained in the step (4) into a plastic package bag separately, and putting the plastic package bag into a vacuum drying oven at 70 ℃ for drying for 8 hours to obtain the phosphorus-based anion type organic metal frame material lithium-sulfur battery diaphragm E.
Step 6: and (3) assembling the lithium sheet of the battery diaphragm E and S@CNT composite anode material and the lithium sheet of the cathode material obtained in the step (5) into a lithium sulfur battery, and testing the rate performance (0.5C, 1C, 2C, 3C and 5C currents), the impedance (the frequency is 0.01-1000000 Hz) and the CV (1.7V-2.7V) under different currents, wherein the scanning rate is 0.001V/s.
As shown in fig. 2, is a phosphorus-based anionic organometallic framework material (PO 3 ) Is an X-ray diffraction pattern of (c). The crystal peak and standard curve of the crystal material can be clearly seen in the XRD pattern to be basically comparedAnd consistent. This also demonstrates that the phosphorus-based anionic organometallic framework material (PO 3) has been successfully prepared.
As shown in fig. 3, lithium sulfur battery separator assembled with phosphor-based anion-type organometallic frame material lithium sulfur battery separator at a scan rate of 0.001V/s (PO 3 -LSB S ) Has a pair of redox peaks. The redox reaction of S in the charge and discharge process of the material is disclosed, and the material has good electrochemical activity.
As shown in fig. 4, a lithium sulfur battery (PO) assembled by a lithium sulfur battery separator made of a phosphorus-based anion type organic metal frame material according to the present invention 3 -LSB S ) Electrochemical Impedance (EIS). And judging the charge transfer resistance and the Walberg impedance of the material by semicircular of the EIS curve in a high frequency region and oblique lines in a low frequency region. Electrochemical resistance and capacitance performance are evaluated by using EIS curves, and the radius of a semicircle of an impedance spectrum represents the interface resistance of an electrolyte and an electrode, and the larger the semicircle in the impedance graph is, the larger the impedance is, and the poorer the electrochemical performance of a battery is. The cell is visually seen to have a small electrochemical impedance by means of fig. 4.
As shown in FIG. 5, a lithium sulfur battery (PO 3-LSB) assembled by a lithium sulfur battery diaphragm made of a phosphorus-based anion type organic metal frame material according to the invention S ) Is a multiplying factor of (2). The specific capacity of the lithium sulfur battery under different currents can be obtained through the multiplying power graph. Compared with the lithium sulfur battery prepared by the traditional method, the lithium sulfur battery (PO 3-LSB S ) At a large rated capacity of 1C, 2C, 3C, even 5C, a higher specific capacity is possessed.
As shown in FIG. 6, a lithium sulfur battery (PO 3-LSB) assembled by a lithium sulfur battery diaphragm made of a phosphorus-based anion type organic metal frame material according to the invention S ) The specific capacity long cycle chart is used for evaluating the change condition of the specific capacity of the battery after the battery is subjected to a plurality of charge and discharge cycles and the maintenance condition of coulombic efficiency, wherein the coulombic efficiency refers to the ratio of the discharge capacity of the battery to the charge capacity in the same cycle, and theoretically, the closer the charge and discharge capacity is, the better the electrochemical performance of the battery is. The cell is shown after 300 cycles at 3C capacitanceThe specific capacity of 580mAh/g is still maintained and the coulombic efficiency approaches 100% during cycling.
Claims (9)
1. The preparation method of the lithium sulfur battery based on the phosphorus-based anion frame polymer diaphragm coating is characterized by comprising the following specific operation steps:
step 1: sequentially weighing zinc nitrate hexahydrate solid and pentamethyltetrazole powder, adding the zinc nitrate hexahydrate solid and pentamethyltetrazole powder into a polytetrafluoroethylene reaction kettle containing N, N-dimethylformamide solution, continuously adding phosphorous acid solution, stirring at room temperature until the solution is uniform and transparent, placing the solution into the reaction kettle to react for 3 days at 85 ℃, then washing the solution with methanol for at least three times, and centrifugally drying to obtain a phosphorus-based anion frame-type metal tetrazole crystalline material A;
step 2: mixing the phosphorus-based anion frame-type metal tetrazole crystalline material A obtained in the step 1, conductive carbon black and a binder in an agate mortar for grinding, and continuously adding N-methyl pyrrolidone into the mortar until uniform slightly sticky black paste B is formed;
step 3: cutting a diaphragm, fixing the diaphragm on a clean and flat glass plate sterilized by alcohol, scraping the black paste B obtained in the step 2 on the surface of the diaphragm by a film scraper, transferring the obtained modified diaphragm and the glass plate into a vacuum drying oven, and drying to obtain a uniform modified diaphragm C;
step 4: taking out the modified diaphragm C obtained in the step 3, and cutting the diaphragm C into a wafer by a tablet press to obtain a modified battery diaphragm D;
step 5: the modified battery diaphragm D obtained in the step 4 is separately filled into a plastic package bag, and is placed into a vacuum drying oven to obtain a phosphorus-based anion type organic metal frame material lithium sulfur battery diaphragm E;
step 6: and (3) assembling the battery diaphragm E obtained in the step (5) with a sulfur-loaded carbon nano tube composite anode material and a sulfur-loaded carbon nano tube composite cathode material lithium sheet into a lithium sulfur battery, and testing the rate capability, impedance and CV under different currents.
2. The method for preparing a lithium sulfur battery based on a phosphorus-based anion frame polymer membrane coating according to claim 1, wherein the mass ratio of zinc nitrate hexahydrate solid to pentamethyltetrazole powder in the step 1 is 12:5, and the volume ratio of phosphorous acid solution to solvent N, N-dimethylformamide solution is 100:3.
3. The method for preparing a lithium-sulfur battery based on a phosphorus-based anionic frame polymer separator coating according to claim 1, wherein the zinc nitrate hexahydrate in step 1 can be replaced by any one of zinc chloride and zinc acetate.
4. The method for preparing a lithium-sulfur battery based on a phosphorus-based anionic frame polymer membrane coating according to claim 1, wherein in the step 2, the mass ratio of the anionic frame-type metal tetrazole crystalline material A, the conductive carbon black and the binder is 8:1:1, and the grinding time is at least 30min.
5. The method for preparing a lithium-sulfur battery based on a phosphorus-based anion frame polymer membrane coating according to claim 1, wherein the vacuum drying temperature in the step 3 is 60-70 ℃ and the drying time is not less than 12h.
6. The method for preparing a lithium-sulfur battery based on a phosphorus-based anionic frame polymer separator coating according to claim 1, wherein the diameter of the cut pieces in step 4 is 16mm.
7. The method for preparing a lithium-sulfur battery based on a phosphorus-based anionic frame polymer membrane coating according to claim 1, wherein the vacuum drying temperature in the step 5 is 60-70 ℃ and the drying time is 8-12 h.
8. The method for preparing a lithium-sulfur battery based on a phosphorus-based anionic frame polymer separator coating according to claim 1, wherein the assembled lithium-sulfur battery in step 6 is tested for electrochemical performance: the multiplying power performance is tested under different currents, the currents are set to be 0.5C, 1C, 2C, 3C and 5C, the parameter frequency of the test is 0.01-1000000Hz when the electrochemical impedance is tested, the cyclic voltammetry test voltage is 1.7V-2.7V, and the scanning rate is 0.001V/s.
9. The method of preparing a lithium sulfur battery based on a coating of a phosphorus-based anionic frame polymer separator according to claim 1, wherein the separator in step 3 is a celgard2400 separator.
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