CN116417615A - Metal battery negative electrode material, preparation method and application thereof - Google Patents
Metal battery negative electrode material, preparation method and application thereof Download PDFInfo
- Publication number
- CN116417615A CN116417615A CN202310262087.9A CN202310262087A CN116417615A CN 116417615 A CN116417615 A CN 116417615A CN 202310262087 A CN202310262087 A CN 202310262087A CN 116417615 A CN116417615 A CN 116417615A
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- Prior art keywords
- carbon fiber
- fibers
- metal
- optionally
- porous carbon
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 77
- 239000002184 metal Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000007773 negative electrode material Substances 0.000 title claims description 27
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 147
- 239000004917 carbon fiber Substances 0.000 claims abstract description 147
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000010405 anode material Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 239000006185 dispersion Substances 0.000 claims abstract description 24
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
- 238000004062 sedimentation Methods 0.000 claims abstract description 9
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 8
- 239000000835 fiber Substances 0.000 claims description 52
- 239000011148 porous material Substances 0.000 claims description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000009987 spinning Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 238000010041 electrostatic spinning Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- -1 aluminum ion Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001523 electrospinning Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 229920003043 Cellulose fiber Polymers 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 108010010803 Gelatin Proteins 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 108010073771 Soybean Proteins Proteins 0.000 claims description 5
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- 235000019322 gelatine Nutrition 0.000 claims description 5
- 235000011852 gelatine desserts Nutrition 0.000 claims description 5
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 5
- 229920005610 lignin Polymers 0.000 claims description 5
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 150000002484 inorganic compounds Chemical class 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 3
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- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920002307 Dextran Polymers 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002494 Zein Polymers 0.000 claims description 2
- 229940081735 acetylcellulose Drugs 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910001430 chromium ion Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 229960002086 dextran Drugs 0.000 claims description 2
- 229940050549 fiber Drugs 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 229940001941 soy protein Drugs 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- 239000005019 zein Substances 0.000 claims description 2
- 229940093612 zein Drugs 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 7
- 150000002739 metals Chemical class 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 13
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000000151 deposition Methods 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
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- 238000011056 performance test Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
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- 235000019710 soybean protein Nutrition 0.000 description 3
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- 238000006243 chemical reaction Methods 0.000 description 2
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- 239000003365 glass fiber Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 101150047356 dec-1 gene Proteins 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
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Classifications
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
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- D—TEXTILES; PAPER
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- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
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- H01M10/052—Li-accumulators
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to the technical field of metal batteries, in particular to a metal battery anode material and a preparation method and application thereof. The preparation method comprises the following steps: dispersing porous carbon fibers and non-carbon fibers in a solvent to obtain a mixed dispersion; removing the solvent from the mixed dispersion; wherein the dispersibility and/or sedimentation rate of the porous carbon fibers in the solvent is different from the dispersibility and/or sedimentation rate of the non-carbon fibers in the solvent; the porous carbon fiber is doped with a hetero element, and the non-carbon fiber is doped with a metal ion. The metal battery anode material prepared by the method has a self-supporting three-dimensional gradient frame structure, and the three-dimensional gradient frame structure can accommodate more metals to be deposited rapidly and uniformly and can effectively inhibit metal dendrite growth; in addition, the non-carbon fiber forms the supporting layer, so that the electrode has good thermal stability, and the improvement of electrochemical performance and safety performance of a metal battery system is facilitated.
Description
Technical Field
The invention relates to the technical field of metal batteries, in particular to a metal battery anode material and a preparation method and application thereof.
Background
With the continuous development and utilization of traditional energy, the problems of resource exhaustion, environmental pollution and the like are increasingly severe, and the clean and sustainable energy source such as electric energy storage is increasingly focused on in various fields. However, with the updating of electric equipment, even the lithium ion secondary battery which is most widely applied and has relatively good performance at present, the requirements of the electric equipment on the aspects of quick charge, cycle life, energy density and the like cannot be met gradually. Therefore, development of the next generation of high efficiency energy storage devices is urgent.
Among the many energy storage devices, the metal battery has a higher energy density and a lower electrode potential because the metal battery directly adopts the metal as the negative electrode, so that the metal battery has a remarkable advantage in the energy storage devices. Unlike the reaction mechanism of the ion battery, the deposition and stripping reaction of metal occurs on the negative side of the metal battery. In the charge and discharge process, the battery generally runs at constant current density, the current flowing through the electrodes at two sides is the same, however, the positive electrode is generally of a porous structure, the electric field distribution is uniform, the metal negative electrode is of a non-porous structure, and the surface can generate extremely high local current density, so that the local electric field intensity is uneven, metal dendrites are caused to grow on the metal negative electrode, the SEI film is unstable, side reactions of the metal negative electrode and electrolyte are aggravated, and finally the safety and the energy utilization rate of a battery system are influenced.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect of metal dendrite growth of the metal battery cathode in the prior art, thereby providing a metal battery cathode material, and a preparation method and application thereof.
Therefore, the invention provides a preparation method of a metal battery anode material, which comprises the following steps:
dispersing porous carbon fibers and non-carbon fibers in a solvent to obtain a mixed dispersion;
removing the solvent from the mixed dispersion;
wherein the dispersibility and/or sedimentation rate of the porous carbon fibers in the solvent is different from the dispersibility and/or sedimentation rate of the non-carbon fibers in the solvent; the porous carbon fiber is doped with a hetero element, and the non-carbon fiber is doped with a metal ion.
Optionally, the removing the solvent in the mixed dispersion liquid comprises:
the mixed dispersion is subjected to suction filtration or freeze drying.
Optionally, the porous carbon fiber has a porosity of 1-30%, a pore diameter of 0.0001-100 μm and a pore volume of 0.5-5 cm 3 Per gram, a specific surface area of 50 to 4000m 2 /g；
Optionally, the hetero element includes at least one of an oxygen element, a nitrogen element, a sulfur element, a chlorine element, a fluorine element, and a phosphorus element;
optionally, the weight of the hetero element accounts for 0.5-20% of the weight of the porous carbon fiber.
Optionally, the preparation process of the porous carbon fiber comprises the following steps:
taking a carbon fiber precursor, and performing first electrostatic spinning and carbonization treatment;
optionally, the conditions of the first electrospinning include: the spinning temperature is 20-80 ℃, the spinning time is 1-10 h, the positive pressure is 10-20 kV, the negative pressure is-10 to-2 kV, the receiving distance is 10-30 cm, and the propelling speed is 0.05-0.30 mm/min;
optionally, the carbonization process includes: carbonizing at 400-800 deg.c in the atmosphere of protecting gas for 1-3 hr;
optionally, the carbon fiber precursor comprises at least one of gelatin, lignin fiber, soy protein, zein, cellulose acetate, and dextran;
optionally, before the first electrospinning is performed, an operation of adding an inorganic compound including at least one of potassium sulfide, sodium sulfide, potassium chloride, potassium nitrate, sodium fluoride, and potassium dihydrogen phosphate;
optionally, the particle size of the inorganic compound is 1-100 μm, and the adding amount of the inorganic compound is 6-40% of the weight of the carbon fiber precursor in parts by weight.
Optionally, the non-carbon fiber has a porosity of 0.2-5%, a pore diameter of 5-100 μm, and a pore volume of 0.05-0.3 cm 3 Per gram, a specific surface area of 1 to 50m 2 /g；
Optionally, the weight of the metal ions accounts for 0.5-20% of the weight of the non-carbon fibers;
optionally, the metal ions include at least one of lithium ion, sodium ion, potassium ion, magnesium ion, aluminum ion, zinc ion, iron ion, nickel ion, cobalt ion, and chromium ion;
the non-carbon fibers include at least one of hydroxyapatite fibers, cellulose fibers, perovskite fibers, metal sulfide fibers, metal oxide fibers, PVDF fibers, PEO fibers, and PAN fibers.
Optionally, the process of doping the metal ions in the non-carbon fiber includes the steps of:
soaking the non-carbon fiber in a solution of metal salt for 10-20 h, taking out and drying; or,
taking raw materials for forming the non-carbon fibers, mixing the raw materials with metal salt, and carrying out second electrostatic spinning;
optionally, the metal salt comprises at least one of chloride, sulfide, sulfate, nitrate, perchlorate, hexafluorophosphate, trifluoromethane sulfonate, and tetrafluoroborate of lithium, sodium, potassium, magnesium, aluminum, zinc, iron, nickel, cobalt, chromium;
optionally, the concentration of the metal salt in the solution is from 0.0001g/mL to 0.1g/mL, preferably from 0.0005g/mL to 0.05g/mL;
optionally, the conditions of the second electrospinning include: the spinning temperature is 20-30 ℃, the spinning time is 2-5 h, the positive pressure is 15-30 kV, the negative pressure is-10 to-1 kV, the receiving distance is 15-30 cm, and the propelling speed is 0.10-0.30 mm/min.
Illustratively, for hydroxyapatite fibers, cellulose fibers, and perovskite fibers, the metal ions may be doped by the impregnation method described above; for metal sulfide fibers, metal oxide fibers, PVDF fibers, PEO fibers, and PAN fibers, the metal ions may be doped using the electrospinning method described above, and the raw material for forming the non-carbon fibers may be PEO, PVDF, PAN, metal oxide, or metal sulfide.
Optionally, the dispersing the porous carbon fiber and the non-carbon fiber in the solvent to obtain a mixed dispersion liquid comprises:
placing the porous carbon fibers and the non-carbon fibers in the solvent, and performing ultrasonic treatment for 1.5-3 hours to obtain the mixed dispersion liquid;
optionally, the weight ratio of the porous carbon fiber to the non-carbon fiber is (1-10): (1-100), preferably (1-50);
optionally, the weight ratio of the porous carbon fiber to the solvent is 1 (100-10000), preferably 1 (1000-6000);
optionally, the solvent comprises at least one of ethanol, methanol, water, diethyl ether, acetone, N-methylpyrrolidone, and ethyl acetate.
The invention also provides a metal battery anode material prepared by the preparation method, the metal battery anode material has a three-dimensional fibrous structure, the porosity of the metal battery anode material is 0.5-25%, the aperture of the metal battery anode material is 0.1 nm-100 mu m, and the pore volume of the metal battery anode material is 0.1-3 cm 3 Per gram, the specific surface area is 10-3000 cm 2 And/g, the length-diameter ratio of the fiber is (100-10000): 1.
The invention also provides a metal battery negative electrode, which comprises the metal battery negative electrode material.
The invention also provides a metal battery, which comprises the metal battery anode material or the metal battery anode.
The technical scheme of the invention has the following advantages:
1. according to the preparation method of the metal battery anode material, firstly, porous carbon fibers and non-carbon fibers with different dispersibility and/or sedimentation speed are dispersed in a solvent, and then the solvent is removed, so that the metal battery anode material is prepared. Wherein, due to the different dispersibility and/or sedimentation speed of the two fibers in the solvent, the two fibers show a layering trend in the mixed dispersion liquid, and the concentration of the two fibers in the mixed dispersion liquid gradually increases along the opposite direction, so that the two fibers in the prepared metal battery anode material also have a layering trend, but the two fibers respectively extend into the fiber structures of each other at the contact part, and the content of the porous carbon fibers gradually decreases along the direction from the porous carbon fiber layer to the non-carbon fiber layer, but the content of the non-carbon fibers gradually increases. That is, the metal battery anode material prepared by the method of the invention has a self-supporting three-dimensional gradient frame structure, and the three-dimensional gradient frame structure can accommodate more metals for rapid and uniform deposition and can effectively inhibit metal dendrite growth; in addition, the non-carbon fiber forms the supporting layer, so that the electrode has good thermal stability, and the improvement of electrochemical performance and safety performance of a metal battery system is facilitated.
Further, in the prepared metal battery anode material, the porous carbon fiber is used as a conductive fiber, so that an efficient electron transmission channel can be provided in the processes of metal deposition and stripping; the abundant pore structure can be used as an electrolyte buffer tank, so that the diffusion of metal ions can be promoted, and the ion transmission capacity can be improved; the doped hetero elements can provide rich metal-philic sites, so that metal can be rapidly and uniformly deposited on the surface of the porous carbon fiber, and metal dendrite growth caused by metal accumulation in the porous carbon fiber is effectively avoided; along the direction of the non-carbon fiber layer to the porous carbon fiber layer, the porous carbon fiber is gradually increased, namely the metal-philic sites are gradually increased, so that metal ions can be effectively induced to be preferentially deposited at the bottom of the anode material (namely the bottom of the porous carbon fiber layer), and further the metal ions are effectively inhibited from being deposited at the top of the anode material (namely the top of the non-carbon fiber layer), and the growth of metal dendrites can be further prevented;
the non-carbon fiber is used as a supporting layer to cover the surface of the porous carbon fiber layer, so that the mechanical property and the flame retardant property of the anode material can be effectively improved, the growth of metal dendrites can be inhibited through the physical restraint effect, and meanwhile, the doped metal ions can provide an efficient ion transmission channel in the deposition and stripping processes of metals.
2. According to the preparation method of the metal battery anode material, provided by the invention, the self-supporting metal battery anode material with the three-dimensional gradient frame structure can be obtained by utilizing different dispersibility and/or sedimentation speeds of two fibers in a solvent through a one-step simple suction filtration or freeze drying mode, so that the preparation method is simple and efficient in process, safe and environment-friendly, low in cost and good in reproducibility, and the prepared anode material is in a continuous state between layers, good in connectivity and good in conductivity.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The metal battery anode material is prepared according to the following method:
(1) Preparation of porous carbon fiber:
taking gelatin aqueous solution with mass percentage concentration of 15% as spinning solution, and carrying out electrostatic spinning, wherein the spinning temperature of the electrostatic spinning is 65 ℃, the spinning time is 8 hours, the positive pressure is 14kV, the negative pressure is-5 kV, the receiving distance is 20cm, and the propelling speed is 0.2mm/min; and after the electrostatic spinning is finished, placing the obtained product in a protective gas atmosphere, and carrying out heat preservation and carbonization for 1.5 hours at 700 ℃ to obtain the gelatin carbon fiber serving as the porous carbon fiber.
The prepared porous carbon fiber is doped with oxygen element and nitrogen element, wherein the doping amount of the oxygen element is 5.4 percent of the weight of the porous carbon fiber, and the doping amount of the nitrogen element is 2.4 percent of the weight of the porous carbon fiber; the porosity of the porous carbon fiber is 25%, the pore diameter is 0.005-20 mu m, and the pore volume is 0.89cm 3 Per gram, specific surface area of 1250m 2 /g。
(2) Preparation of non-carbon fibers:
1g of hydroxyapatite is taken to be placed in 100mL of ethanol solution dissolved with 0.15g of lithium chloride, and after being soaked for 15h, the hydroxyapatite fiber doped with lithium ions is obtained and taken out for drying, and is used as non-carbon fiber.
The prepared non-carbon fiber is doped with lithium ions, the doping amount is 4.2 percent of the weight of the non-carbon fiber, the porosity is 1.1 percent, the pore diameter is 5-50 mu m, and the pore volume is 0.08cm 3 Per gram, specific surface area of 32m 2 /g。
(3) Preparation of a negative electrode material:
respectively weighing 20mg of the porous carbon fiber and 100mg of the non-carbon fiber (the weight ratio of the porous carbon fiber to the non-carbon fiber is 1:5), adding the materials into a beaker containing 150mL of ethanol solution, and then placing the beaker into an ultrasonic machine for ultrasonic treatment for 3 hours until the materials are uniformly mixed to obtain mixed dispersion liquid; and (3) constructing a suction filtration device, performing suction filtration on the prepared mixed dispersion liquid to form a film by utilizing the different dispersibility of the two fibers, taking down and drying to obtain the negative electrode material with the three-dimensional gradient frame structure.
The prepared anode material comprises a porous carbon fiber layer and a non-carbon fiber layer, wherein the porous carbon fiber layer and the non-carbon fiber layer are in contact with each other, the two fibers respectively extend into a fiber structure of each other at contact parts, the content of the porous carbon fiber is gradually reduced along the direction from the porous carbon fiber layer to the non-carbon fiber layer, and the content of the non-carbon fiber is gradually increased; wherein the lithium element, the oxygen element and the nitrogen element are doped, the overall porosity of the material is 15%, the aperture is 5 nm-50 mu m, and the pore volume is 0.28cm 3 Per gram, specific surface area 550m 2 The length-diameter ratio of the fiber is in the range of 4000-6000:1.
(4) Performance testing
Cutting the prepared anode material into round pieces with the diameter of 14mm, taking a lithium metal sheet as a counter electrode, taking PP as a diaphragm, and taking 1M LiPF as the anode 6 (EC/DEC 1:1) is electrolyte, and is assembled into a half cell; at 1mA/cm 2 Constant current discharge to deposit lithium at a current density of 1mAh/cm 2 The cut-off voltage is 1V, and the overpotential is 25mV obtained by testing; next, it was subjected to a lithium deposition peel test at 1mA/cm 2 Is 1mAh/cm 2 200 cycles of deposition/stripping capacity, the coulombic efficiency retention was measured to be 96.5%; at 1mA/cm 2 Is 1mAh/cm 2 The voltage can still be kept in a stable state after 450h of the deposition/stripping capacity, which indicates that the long-cycle performance is good.
As is apparent from the above performance test results, the anode material prepared by the above method exhibits excellent electrochemical properties when used as a lithium metal matrix.
Example 2
A metal battery negative electrode material was prepared according to the method of example 1, except that the porous carbon fiber in this example was lignin carbon fiber, and the non-carbon fiber was cellulose fiber. Specifically, the preparation methods of the porous carbon fiber and the non-carbon fiber in this embodiment are as follows:
(1) Preparation of porous carbon fiber:
and (3) taking a lignin aqueous solution with the mass percentage concentration of 15% as a spinning stock solution, and carrying out electrostatic spinning and carbonization treatment according to the method of the step (1) in the example 1 to obtain lignin carbon fibers serving as porous carbon fibers.
The porous carbon fiber prepared by the method is doped with oxygen element, the doping amount is 7.2 percent of the weight of the porous carbon fiber, the porosity is 26 percent, the pore diameter is 0.005-25 mu m, and the pore volume is 0.86cm 3 Per gram, specific surface area 1132m 2 /g。
(2) Preparation of non-carbon fibers:
1g of cellulose fiber is taken and placed in 100mL of ethanol solution dissolved with 0.15g of lithium chloride, and after soaking for 15h, the cellulose fiber doped with lithium ions is obtained and taken out for drying, so as to be used as non-carbon fiber.
The prepared non-carbon fiber is doped with lithium ions, the doping amount is 4.3 percent of the total amount of the non-carbon fiber, the porosity is 1.1 percent, the pore diameter is 10-60 mu m, and the pore volume is 0.07cm 3 Per gram, specific surface area of 28m 2 /g。
The anode material prepared in this example is doped with lithium element and oxygen element, the overall porosity of the material is 14%, the pore diameter is 5 nm-60 μm, and the pore volume is 0.25cm 3 Per gram, a specific surface area of 522m 2 The length-diameter ratio of the fiber is in the range of 3000-6000:1.
The performance of the negative electrode material prepared in this example was tested according to the method of example 1, and the overpotential thereof was measured to be 27mV, the coulombic efficiency retention rate after 200 cycles was 94.8%, the voltage remained stable after 450 hours of cycle, and the long cycle performance was good.
Example 3
A metal battery negative electrode material was prepared according to the method of example 1, except that the porous carbon fiber in this example was a soybean protein carbon fiber and the non-carbon fiber was a PAN fiber. Specifically, the preparation methods of the porous carbon fiber and the non-carbon fiber in this embodiment are as follows:
(1) Preparation of porous carbon fiber:
the electrostatic spinning and carbonization treatment were performed in the same manner as in step (1) of example 1 using a 15% by mass aqueous solution of soybean protein as a spinning dope to obtain a soybean protein carbon fiber as a porous carbon fiber.
The prepared porous carbon fiber is doped with nitrogen element, the doping amount is 6.9 percent, the porosity is 22 percent, the pore diameter is 0.005-30 mu m, and the pore volume is 0.78cm 3 Per gram, specific surface area of 989m 2 /g。
(2) Preparation of non-carbon fibers:
preparing a PAN solution with the mass percent concentration of 10% by taking DMF as a solvent, simultaneously doping lithium chloride accounting for 2% of the mass of PAN, preparing a spinning solution, and carrying out electrostatic spinning to obtain PAN fibers doped with lithium ions, wherein the spinning temperature of the electrostatic spinning is 25 ℃, the spinning time is 5h, the positive pressure is 15kV, the negative pressure is-8 kV, the receiving distance is 25cm, and the propelling speed is 0.20mm/min.
The prepared non-carbon fiber is doped with lithium ions, the doping amount is 3.8 percent, the porosity is 0.9 percent, the pore diameter is 5-60 mu m, and the pore volume is 0.07cm 3 Per gram, specific surface area of 26m 2 /g。
The anode material prepared in this example is doped with lithium element and oxygen element, the overall porosity of the material is 13%, the pore diameter is 5 nm-60 μm, and the pore volume is 0.24cm 3 Per gram, specific surface area of 488m 2 And the length-diameter ratio of the fiber is in the range of 2000-5000:1.
The performance of the negative electrode material prepared in this example was tested according to the method of example 1, and the overpotential thereof was measured to be 29mV, the coulombic efficiency retention rate after 200 cycles was 94.5%, the voltage remained stable after 450 hours of cycle, and the long cycle performance was good.
Example 4
A metal battery anode material was prepared in the same manner as in example 1 except that in the preparation of porous carbon fiber in this example, 0.6g of potassium sulfide was added to the gelatin aqueous solution to control the pore structure of the obtained carbon fiber while achieving incorporation of sulfur element.
The porous carbon fiber prepared by the method is doped with oxygen element, nitrogen element and sulfur element, wherein the doping amount of the oxygen element is 4.8 percent of the weight of the porous carbon fiber, the doping amount of the nitrogen element is 2.1 percent of the weight of the porous carbon fiber, and the doping amount of the sulfur element is 1.9 percent of the weight of the porous carbon fiber; the porosity of the porous carbon fiber is 29%, the pore diameter is 0.005-20 mu m, and the pore volume is 1.08cm 3 Per gram, specific surface area of 1780m 2 /g。
The anode material prepared in this example is doped with lithium element, oxygen element, nitrogen element and sulfur element, the overall porosity of the material is 23%, the pore diameter range is 0.2 nm-50 μm, and the pore volume is 2.0cm 3 Per g, specific surface area 2001m 2 And the length-diameter ratio of the fiber is in the range of (800-5000): 1.
The performance of the negative electrode material prepared in this example was tested according to the method of example 1, and the overpotential was measured to be 18mV, the coulombic efficiency retention rate after 200 cycles was 99.2%, the voltage remained stable after 500 hours of cycle, and the long cycle performance was good.
Example 5
A metal battery anode material was prepared according to the method of example 1, except that in the present example, the weight ratio of the porous carbon fiber to the non-carbon fiber was 1:20, that is, the weighed amount of the porous carbon fiber in step (3) was 20mg, and the weighed amount of the non-carbon fiber was 400mg.
The anode material prepared in this example is doped with lithium element, oxygen element and nitrogen element, the overall porosity of the material is 7%, the pore diameter range is 8-60 nm, and the pore volume is 0.26cm 3 Per gram, specific surface area of 232m 2 The length-diameter ratio of the fiber is in the range of 4000 to 7000 to 1.
The performance of the negative electrode material prepared in this example was tested according to the method of example 1, and the overpotential thereof was measured to be 31mV, the coulombic efficiency retention rate after 200 cycles was 93.5%, the voltage remained stable after 450 hours of cycle, and the long cycle performance was good.
Example 6
A metal battery negative electrode material was prepared in the same manner as in example 1, except that in the preparation of the non-carbon fiber in this example, the amount of lithium chloride used was 0.75g.
The prepared non-carbon fiber is doped with lithium ions, the doping amount is 7.2 percent of the weight of the non-carbon fiber, the porosity is 1.9 percent, the pore diameter is 5-60 mu m, and the pore volume is 0.11cm 3 Per gram, specific surface area of 50m 2 /g。
The anode material prepared in this example is doped with lithium element, oxygen element and nitrogen element, the overall porosity of the material is 17%, the pore diameter range is 8 nm-65 μm, and the pore volume is 0.30cm 3 Per gram, a specific surface area of 560m 2 The length-diameter ratio of the fiber is in the range of 500-4000:1.
The performance of the negative electrode material prepared in this example was tested according to the method of example 1, and the overpotential was measured to be 30mV, the coulombic efficiency retention rate after 200 cycles was 94.2%, the voltage remained stable after 450 hours of cycle, and the long cycle performance was good.
Example 7
A metal battery negative electrode material was prepared as in example 1, except that in this example, the same amount of zinc nitrate was used in place of lithium chloride in the preparation of the non-carbon fiber. The prepared non-carbon fiber is doped with zinc ions, the doping amount is 8.7 percent, the porosity is 2 percent, the aperture is 8-65 mu m, and the pore volume is 0.1cm 3 Per gram, specific surface area of 45m 2 /g。
The anode material prepared in this example is doped with zinc element, oxygen element and nitrogen element, the overall porosity of the material is 18%, the pore diameter range is 5 nm-65 μm, and the pore volume is 0.42cm 3 Per gram, specific surface area 677m 2 The length-diameter ratio of the fiber is in the range of 3000-6000:1.
Cutting the anode material prepared in this example into 14mm diameter round pieces, using zinc sheet as counter electrode, and glass fiber as spacerFilm of ZnSO at a concentration of 2mol/L 4 The solution is electrolyte, and the half-cell is assembled; at 1mA/cm 2 Constant current discharge to deposit zinc at a current density of 1mAh/cm 2 The cut-off voltage was 0.5V, and the overpotential was tested to be 25mV; it was then subjected to a zinc deposition strip test at 1mA/cm 2 ，1mAh/cm 2 The retention rate of coulomb efficiency after 200 circles of circulation is 97.8 percent, and the performance is excellent; at a current of 1mA/cm 2 Deposition/stripping capacity of 1mAh/cm 2 The voltage can still keep stable state after 400 hours of circulation under the condition of (2) and the long-circulation performance is good.
Example 8
A metal battery negative electrode material was prepared as in example 1, except that in this example, the lithium chloride was replaced with an equal amount of sodium sulfide when preparing the non-carbon fiber. The prepared non-carbon fiber is doped with sodium ions, the doping amount is 4.2 percent, the porosity is 0.8 percent, the aperture is 15-60 mu m, and the pore volume is 0.06cm 3 Per gram, specific surface area of 18m 2 /g。
The anode material prepared in this example is doped with sodium element, oxygen element and nitrogen element, the overall porosity of the material is 12%, the pore diameter range is 5 nm-60 μm, and the pore volume is 0.39cm 3 Per gram, specific surface area of 401m 2 And/g, the length-diameter ratio of the fiber is in the range of 3000-5000:1.
Cutting the anode material prepared in the embodiment into a wafer with the diameter of 14mm, taking a sodium metal sheet as a counter electrode, taking glass fiber as a diaphragm, and taking NaPF6 (100% diglyme) as electrolyte, and assembling the wafer into a half cell; at 0.5mA/cm 2 Constant current discharge at current density to deposit sodium, set cut-off capacity 0.5mAh/cm 2 Cut-off voltage 0.5V, test its overpotential is 23mV; it was then subjected to a sodium deposition peel test at 0.5mA/cm 2 ，0.5mAh/cm 2 The retention rate of coulomb efficiency after 200 circles of circulation is 96.9%, and the performance is excellent; at a current of 0.5mA/cm 2 Deposition/stripping capacity of 0.5mAh/cm 2 The voltage can still keep a stable state after the cycle is carried out for 300 hours under the condition of (2) and the long-cycle performance is good.
Example 9
A metal battery anode material was prepared in the same manner as in example 1, except that in the preparation of the anode material in this example, the ethanol solution was replaced with an equal amount of water and used as a solvent to improve the dispersion of the two fibers in the mixed dispersion.
The anode material prepared in this example is doped with lithium element, oxygen element and nitrogen element, the overall porosity of the material is 15%, the pore diameter range is 5 nm-50 μm, and the pore volume is 0.27cm 3 Per gram, specific surface area 445m 2 The length-diameter ratio of the fiber is in the range of 4000-6000:1.
The negative electrode material prepared in this example was subjected to performance test according to the method of example 1, and the overpotential thereof was measured to be 28mV, the coulombic efficiency retention rate after 200 cycles was 95.4%, the performance was excellent, the voltage remained in a stable state after 400 hours of cycle, and the long cycle performance was good.
Example 10
A negative electrode material for a metal battery was prepared according to the method of example 1, except that in the preparation of the negative electrode material in this example, the suction filtration film forming process was replaced with a freeze drying process, and freeze drying was performed for 36 hours, to obtain a negative electrode material having a three-dimensional gradient frame structure.
The anode material prepared in this example is doped with lithium element, oxygen element and nitrogen element, the overall porosity of the material is 18%, the pore diameter range is 5 nm-100 μm, and the pore volume is 0.51cm 3 Per g, a specific surface area of 812m 2 The length-diameter ratio of the fiber is in the range of 3000-6000:1.
The negative electrode material prepared in this example was subjected to performance test according to the method of example 1, and the overpotential thereof was measured to be 23mV, the coulombic efficiency retention rate after 200 cycles was 98.7%, the performance was excellent, the voltage remained in a stable state after 450 hours of cycle, and the long cycle performance was good.
Comparative example 1
In the comparative example, the anode material is directly prepared by the porous carbon fiber prepared in the step (1) of the example 1, specifically, 120mg of the porous carbon fiber is weighed and added into a beaker containing 150mL of ethanol solution, and then the beaker is placed into an ultrasonic machine for ultrasonic treatment for 3 hours until the mixture is uniformly mixed, so as to obtain a mixed dispersion liquid; and (3) setting up a suction filtration device, performing suction filtration on the prepared mixed dispersion liquid to form a film by utilizing the different dispersibility of the two fibers, taking down and drying to obtain the negative electrode material.
The negative electrode material prepared in this comparative example was subjected to performance test according to the method of example 1, and its overpotential was measured to be 35mV, the coulomb efficiency retention after 200 cycles was 41%, the voltage exceeded the range after 150 hours of cycles, and the test was stopped.
Comparative example 2
In the comparative example, the non-carbon fiber prepared in the step (2) of the example 1 is directly used for preparing the anode material, specifically, 120mg of the non-carbon fiber is weighed and added into a beaker containing 150mL of ethanol solution, and then the beaker is placed into an ultrasonic machine for ultrasonic treatment for 3 hours until the materials are uniformly mixed, so as to obtain mixed dispersion liquid; and (3) setting up a suction filtration device, performing suction filtration on the prepared mixed dispersion liquid to form a film by utilizing the different dispersibility of the two fibers, taking down and drying to obtain the negative electrode material.
The negative electrode material prepared in this comparative example was subjected to performance test according to the method of example 1, and the overpotential thereof was measured to be 48mV, the battery was damaged by 20 cycles of the cycle, the voltage exceeded the range after 30 hours of the cycle, and the test was stopped.
Comparative example 3
The negative electrode material was prepared as follows:
(1) Using the porous carbon fiber prepared in the step (1) of example 1 as a raw material, pressing a porous carbon fiber film with a thickness of 40 μm;
(2) Pressing a non-carbon fiber film with a thickness of 40 μm by using the non-carbon fiber prepared in the step (2) of example 1 as a raw material;
(3) And laminating the porous carbon fiber film and the non-carbon fiber film, and pressing to obtain the anode material.
The negative electrode material prepared in this comparative example was subjected to performance test according to the method of example 1, and the overpotential thereof was measured to be 38mV, the coulomb efficiency retention rate after 200 cycles was 23.4%, and the voltage was overscaled after 450 hours of cycle, and the test was stopped.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The preparation method of the metal battery anode material is characterized by comprising the following steps of:
dispersing porous carbon fibers and non-carbon fibers in a solvent to obtain a mixed dispersion;
removing the solvent from the mixed dispersion;
wherein the dispersibility and/or sedimentation rate of the porous carbon fibers in the solvent is different from the dispersibility and/or sedimentation rate of the non-carbon fibers in the solvent; the porous carbon fiber is doped with a hetero element, and the non-carbon fiber is doped with a metal ion.
2. The method of preparing according to claim 1, wherein said removing the solvent in the mixed dispersion liquid comprises:
the mixed dispersion is subjected to suction filtration or freeze drying.
3. The method according to claim 1 or 2, wherein the porous carbon fiber has a porosity of 1 to 30%, a pore diameter of 0.0001 to 100 μm, and a pore volume of 0.5 to 5cm 3 Per gram, a specific surface area of 50 to 4000m 2 /g；
Optionally, the hetero element includes at least one of an oxygen element, a nitrogen element, a sulfur element, a chlorine element, a fluorine element, and a phosphorus element;
optionally, the weight of the hetero element accounts for 0.5-20% of the weight of the porous carbon fiber.
4. The method according to claim 3, wherein the porous carbon fiber is produced by a process comprising the steps of:
taking a carbon fiber precursor, and performing first electrostatic spinning and carbonization treatment;
optionally, the conditions of the first electrospinning include: the spinning temperature is 20-80 ℃, the spinning time is 1-10 h, the positive pressure is 10-20 kV, the negative pressure is-10 to-2 kV, the receiving distance is 10-30 cm, and the propelling speed is 0.05-0.30 mm/min;
optionally, the carbonization process includes: carbonizing at 400-800 deg.c in the atmosphere of protecting gas for 1-3 hr;
optionally, the carbon fiber precursor comprises at least one of gelatin, lignin fiber, soy protein, zein, cellulose acetate, and dextran;
optionally, before the first electrospinning is performed, an operation of adding an inorganic compound including at least one of potassium sulfide, sodium sulfide, potassium chloride, potassium nitrate, sodium fluoride, and potassium dihydrogen phosphate is further included.
5. The method according to any one of claims 1 to 4, wherein the non-carbon fiber has a porosity of 0.2 to 5%, a pore diameter of 5 to 100 μm, and a pore volume of 0.05 to 0.3cm 3 Per gram, a specific surface area of 1 to 50m 2 /g；
Optionally, the weight of the metal ions accounts for 0.5-20% of the weight of the non-carbon fibers;
optionally, the metal ions include at least one of lithium ion, sodium ion, potassium ion, magnesium ion, aluminum ion, zinc ion, iron ion, nickel ion, cobalt ion, and chromium ion;
optionally, the non-carbon fibers include at least one of hydroxyapatite fibers, cellulose fibers, perovskite fibers, metal sulfide fibers, metal oxide fibers, PVDF fibers, PEO fibers, and PAN fibers.
6. The method of claim 5, wherein the process of doping the non-carbon fibers with the metal ions comprises the steps of:
soaking the non-carbon fiber in a solution of metal salt for 10-20 h, taking out and drying; or,
taking raw materials for forming the non-carbon fibers, mixing the raw materials with metal salt, and carrying out second electrostatic spinning;
optionally, the metal salt comprises at least one of chloride, sulfide, sulfate, nitrate, perchlorate, hexafluorophosphate, trifluoromethane sulfonate, and tetrafluoroborate of lithium, sodium, potassium, magnesium, aluminum, zinc, iron, nickel, cobalt, chromium;
optionally, the concentration of the metal salt in the solution is from 0.0001g/mL to 0.1g/mL, preferably from 0.0005g/mL to 0.05g/mL;
optionally, the conditions of the second electrospinning include: the spinning temperature is 20-30 ℃, the spinning time is 2-5 h, the positive pressure is 15-30 kV, the negative pressure is-10 to-1 kV, the receiving distance is 15-30 cm, and the propelling speed is 0.10-0.30 mm/min.
7. The method according to any one of claims 1 to 6, wherein the dispersing porous carbon fibers and non-carbon fibers in a solvent to obtain a mixed dispersion liquid comprises:
placing the porous carbon fibers and the non-carbon fibers in the solvent, and performing ultrasonic treatment for 1.5-3 hours to obtain the mixed dispersion liquid;
optionally, the weight ratio of the porous carbon fiber to the non-carbon fiber is (1-10): (1-100), preferably (1-50);
optionally, the solvent comprises at least one of ethanol, methanol, water, diethyl ether, acetone, N-methylpyrrolidone, and ethyl acetate.
8. The metal battery anode material prepared by the preparation method of any one of claims 1 to 7, which has a three-dimensional fibrous structure with a porosity of 0.5 to 25%, a pore diameter of 0.1nm to 100 μm and a pore volume of 0.1 to 3cm 3 Per gram, the specific surface area is 10-3000 cm 2 And/g, the length-diameter ratio of the fiber is (100-10000): 1.
9. A metal battery negative electrode, characterized in that the metal battery negative electrode comprises the metal battery negative electrode material of claim 8.
10. A metal battery, characterized in that the metal battery comprises the metal battery anode material of claim 8 or the metal battery anode of claim 9.
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| CN116969432B (en) * | 2023-09-12 | 2024-05-17 | 北京化工大学 | Inorganic super-ion conductor material, preparation method and application thereof, inorganic solid electrolyte membrane and lithium battery |
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