CN115863569A - Plant carbon-supported metal compound nano composite material and preparation method and application thereof - Google Patents
Plant carbon-supported metal compound nano composite material and preparation method and application thereof Download PDFInfo
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- CN115863569A CN115863569A CN202211499216.8A CN202211499216A CN115863569A CN 115863569 A CN115863569 A CN 115863569A CN 202211499216 A CN202211499216 A CN 202211499216A CN 115863569 A CN115863569 A CN 115863569A
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- 150000002736 metal compounds Chemical class 0.000 title claims abstract description 86
- 239000000463 material Substances 0.000 title claims abstract description 40
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 24
- 238000004108 freeze drying Methods 0.000 claims abstract description 22
- 150000003624 transition metals Chemical class 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000003763 carbonization Methods 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- 241000196324 Embryophyta Species 0.000 claims description 116
- 239000002086 nanomaterial Substances 0.000 claims description 59
- 229910052573 porcelain Inorganic materials 0.000 claims description 55
- 238000010438 heat treatment Methods 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 30
- 238000000967 suction filtration Methods 0.000 claims description 28
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 27
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 27
- 239000012300 argon atmosphere Substances 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 230000008014 freezing Effects 0.000 claims description 14
- 238000007710 freezing Methods 0.000 claims description 14
- 239000004033 plastic Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 5
- 229940044175 cobalt sulfate Drugs 0.000 claims description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 5
- -1 nickel nitride Chemical class 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 210000000582 semen Anatomy 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 241000218236 Cannabis Species 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 2
- 235000011201 Ginkgo Nutrition 0.000 claims description 2
- 244000194101 Ginkgo biloba Species 0.000 claims description 2
- 235000008100 Ginkgo biloba Nutrition 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 241000219000 Populus Species 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- 239000005083 Zinc sulfide Substances 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- KSECJOPEZIAKMU-UHFFFAOYSA-N [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] Chemical compound [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] KSECJOPEZIAKMU-UHFFFAOYSA-N 0.000 claims description 2
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 claims description 2
- 239000005539 carbonized material Substances 0.000 claims description 2
- 229910001567 cementite Inorganic materials 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- DBULDCSVZCUQIR-UHFFFAOYSA-N chromium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Cr+3].[Cr+3] DBULDCSVZCUQIR-UHFFFAOYSA-N 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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- 229960000355 copper sulfate Drugs 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 2
- IJCCOEGCVILSMZ-UHFFFAOYSA-L copper;dichlorate Chemical compound [Cu+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O IJCCOEGCVILSMZ-UHFFFAOYSA-L 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- 229940032950 ferric sulfate Drugs 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 150000002333 glycines Chemical class 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- 229940053662 nickel sulfate Drugs 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 2
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- GTQFPPIXGLYKCZ-UHFFFAOYSA-L zinc chlorate Chemical compound [Zn+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O GTQFPPIXGLYKCZ-UHFFFAOYSA-L 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 abstract description 7
- 125000005842 heteroatom Chemical group 0.000 abstract description 6
- 230000001976 improved effect Effects 0.000 abstract description 6
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
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Abstract
The invention relates to a plant carbon-carried metal compound nano composite material, a preparation method and application thereof. According to the invention, inorganic salt is adsorbed by utilizing the capillary action and concentration difference action of plants, and the natural ordered structure and element components of the plants are retained in the freeze-drying carbonization process by virtue of the limited domain supporting action of an inorganic auxiliary agent, so that a smooth insertion and extraction channel is provided for metal ions in the circulation process, and the rapid transmission of the metal ions is ensured; the transition metal oxysalt auxiliary agent is used for inducing the uniform doping of heteroatoms under the actions of template doping and activation to form a hierarchical porous carbon structure, so that a large number of active sites are provided for ions, the uniform deposition of metal is facilitated, and the capacity is effectively improved; meanwhile, the metal compound obtained by reducing the transition metal oxysalt in the carbonization process can induce metal ions to uniformly nucleate on the surface of the transition metal oxysalt, so that the capacity is further improved. Therefore, when the plant carbon-supported metal compound nanocomposite is used as a negative electrode material of a secondary battery, excellent energy storage and quick charge performance is shown.
Description
Technical Field
The invention relates to the technical field of nano composite materials, in particular to a plant carbon-supported metal compound nano composite material and a preparation method and application thereof.
Background
In the face of increasingly intensified energy and environment problems, the popularization and use of clean energy become one of the most effective ways to realize sustainable development. As an energy storage device, a secondary battery can realize storage and utilization of clean energy. However, the performance of the alloy is still further improved, and the cost is still further reduced. Therefore, the development of high-performance, low-cost electrode materials is of great significance for large-scale applications of secondary batteries.
The carbon-based electrode material has the advantages of good electrical conductivity, wide source, stable chemical property, low cost and the like. However, the commercial graphite negative electrode material has the disadvantages of poor cycle performance, low specific capacity and the like. Unlike graphite negative electrode materials, metal compound-loaded carbon nanomaterials can serve as excellent secondary battery negative electrode materials. By virtue of the limited-area supporting effect of the auxiliary agent, the original structure and components of the carbon material can be reserved; the metal compound and the high specific surface area provide a large number of nucleation sites, so that the carbon nanomaterial has high reversible capacity.
The plant is an ideal precursor for preparing the metal compound loaded carbon nano material. The plant has a natural shape structure and chemical components, the natural one-dimensional, two-dimensional and three-dimensional structures of the plant are partially reserved through pyrolysis control, and meanwhile, the non-carbon elements such as oxygen, nitrogen, sulfur, phosphorus and the like contained in the plant can directly realize the in-situ doping of heteroatoms in the pyrolysis process. But still faces a number of problems in the material preparation process. Firstly, the natural micro-nano structure and chemical composition of the plant are difficult to maintain, and the original natural micro-nano structure of the plant loses stability and collapses due to large loss and carbonization reconstruction of organic components. Secondly, the auxiliaries are distributed unevenly in the plant body and are mostly distributed on the surface, so that the auxiliaries are only subjected to pore-forming and doping on the surface of the plant body and are distributed unevenly, and the morphology structure and the chemical composition of the plant-based carbon material are difficult to regulate and control. Therefore, how to design a simple and efficient scheme, the plant is taken as a precursor to accurately regulate and control the morphological structure and chemical components of the carbon material, and the realization of the preparation of the plant carbon-supported metal compound nano material with low cost and high performance has important significance for promoting the large-scale application of the secondary battery.
Disclosure of Invention
The invention aims to solve the technical problems that the prior art cannot effectively solve the technical problems of limited capacity, rapid ion transmission, uneven metal deposition on the surface of an electrode, easy growth of dendrite, irreversible volume expansion, poor safety and the like of a negative electrode material of a secondary metal/ion battery. The invention provides a plant carbon-carried metal compound nano material, which is prepared by soaking plant substances in transition metal oxoacid salt solution, and performing freeze-drying pyrolysis carbonization. According to the invention, inorganic salt is adsorbed by utilizing the capillary action and concentration difference action of plants, and the natural ordered structure and element components of the plants are retained in the freeze-drying carbonization process by virtue of the limited domain supporting action of an inorganic auxiliary agent, so that a smooth insertion and extraction channel is provided for metal ions in the circulation process, and the rapid transmission of the metal ions is ensured; the transition metal oxysalt auxiliary agent is used for inducing the uniform doping of heteroatoms under the effects of template, doping and activation to form a hierarchical porous carbon structure, so that a large number of active sites are provided for ions, the uniform deposition of metal is facilitated, and the capacity is effectively improved; meanwhile, the metal compound obtained by reducing the transition metal oxysalt in the carbonization process can induce metal ions to uniformly nucleate on the surface of the transition metal oxysalt, so that the capacity is further improved. Therefore, when the plant carbon-supported metal compound nano material is used as a negative electrode material of a secondary battery, excellent energy storage and quick charge performance is shown.
In order to solve the technical problems, the invention adopts the following technical scheme: a plant carbon supported metal compound nanocomposite, said nanocomposite uniformly supporting a metal compound, said metal compound comprising: titanium carbide, titanium nitride, titanium oxide, titanium sulfide, vanadium oxide, vanadium sulfide, chromium oxide, chromium sulfide, manganese oxide, iron carbide, iron oxide, iron phosphide, iron sulfide, ferric chloride, cobalt oxide, cobalt phosphide, cobalt sulfide, nickel nitride, nickel oxide, nickel sulfide, copper oxide, copper sulfide, zinc oxide, zinc sulfide, zinc chloride and one or more of same-group metal compounds.
Preferably, the structure of the plant carbon-supported metal compound nanocomposite is a one-dimensional fiber structure, and the length-diameter ratio of the material is 100-10000;
or the structure of the plant carbon-supported metal compound nanocomposite is a two-dimensional structure, and the length-width ratio of the material is 1; the thickness range of the material is 0.01-10 μm, and the thickness-to-width ratio is 1;
or the structure of the plant carbon-supported metal compound nanocomposite is a three-dimensional pipeline structure, and the length-diameter ratio of the material is 10; the diameter range is 0.1-10 μm;
or the structure of the plant carbon-supported metal compound nano composite material is a three-dimensional spherical porous structure, and the diameter range of the material is 1-100 mu m.
Preferably, the plant carbon-supported metal compound nanocomposite material has 0.1 to 10at.% of nitrogen;
and/or, the atomic percent of oxygen is 1-15at.%;
and/or, the atomic percentage of sulfur is 1-20at.%;
and/or, the atomic percent of phosphorus is 0.1-10at.%;
and/or the atomic percent of the metal is 1-20at.%.
Preferably, the pore diameter of the plant carbon-supported metal compound nanocomposite is in the range of 0.001-10 μm;
and/or a pore volume in the range of 0.01cm 3 /g-1cm 3 /g；
And/or a specific surface area of 5m 2 /g-5000m 2 /g。
The invention also provides a preparation method of the plant carbon-carried metal compound nano composite material, which comprises the following steps: soaking the plant matter in transition metal oxoacid salt solution, and then sequentially drying, carbonizing, washing and drying the plant matter to obtain the plant carbon-carried metal compound nano material.
Preferably, the plant material precursor comprises: at least one of radix Sophorae Tonkinensis, caulis Cannabis, pollen, thallus Porphyrae, populus chinensis, cotton, semen glycines, folium Ginkgo, semen Cucurbitae, and corn cob;
the transition metal oxyacid salt includes: at least one of titanium sulfate, manganese sulfate, ferric sulfate, cobalt sulfate, nickel sulfate, copper sulfate, zinc sulfate, chromium nitrate, manganese nitrate, iron nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, copper chlorate, zinc chlorate, vanadium oxalate, an oxyacid salt of an equivalent metal, and the like;
preferably, the concentration of the transition metal oxosalt impregnation solution is in the range of 0.001g/cm 3 -1 g/cm 3 The mass ratio of the plant material precursor to the transition metal oxysalt is 1.
Preferably, the drying process conditions before carbonization comprise one or more of normal temperature drying, vacuum drying, heating drying or freeze drying; more preferably, the freeze-drying process conditions include: and transferring the transition metal oxysalt dipping solution to a plastic culture dish, putting the culture dish into a freeze dryer for pre-freezing for 12 hours, and then freeze-drying for 48 hours.
Preferably, the carbonization process comprises: heating the dried sample to 100-250 ℃ at a heating rate of 1-20 ℃/min in an inert atmosphere in an argon atmosphere, and then preserving heat for 0.5-2h; then heating to 600-2800 ℃ at the same heating rate, and then preserving heat for 1-3h; and taking out the sample when the temperature of the sample is cooled to room temperature. More preferably, the dried sample is placed in a porcelain boat. Placing the porcelain boat in a tube furnace, heating to 150 ℃ at a heating rate of 2.5 ℃/min in an inert atmosphere, and then preserving heat for 30min; then heating to 600 ℃ at the same heating rate, and then preserving heat for 1h; and taking out the sample in the porcelain boat when the temperature of the sample is cooled to room temperature.
And/or, the water washing process comprises: uniformly stirring the carbonized material in water at a rotating speed of 300-500 r/min for 8-12h, and performing suction filtration to obtain a sample for subsequent drying;
and/or the drying treatment temperature is 60-80 ℃, and the drying time is 10-15h.
The invention also protects the application of the plant carbon-carried metal compound nano composite material or the plant carbon-carried metal compound nano material prepared by the method in the negative electrode of a secondary metal/ion battery.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the invention selects natural plants as carbon-based precursors, uses the structural advantages of the plants, uses transition metal oxysalt as an auxiliary agent, soaks the plants in inorganic salt, enables the inorganic salt to be uniformly adsorbed in the plants by the capillary adsorption effect and the concentration difference effect of the system, and plays a role of a limited domain supporting structure by virtue of the inorganic auxiliary agent, so that the original natural ordered structure of the plants can be effectively reserved in the subsequent freeze-drying carbonization process, a smooth transmission channel is provided for ions, the ions are favorably embedded and separated, meanwhile, non-carbon element components contained in the plants are reserved, and the existence of heteroatoms provides additional active sites for the reaction.
2. The plant carbon-carried metal compound nano material provided by the invention selects transition metal oxysalt, and the transition metal oxysalt serving as an auxiliary agent has multiple functions: the transition metal oxysalt as a doping agent can effectively introduce heteroatoms such as phosphorus, sulfur, chlorine and the like, and a large number of active sites are provided. Meanwhile, as a template and an activating agent, a mesoporous and microporous structure can be effectively introduced, so that the material is promoted to form a hierarchical porous carbon structure, the specific surface area of the material is effectively increased, and the capacity is improved.
3. The transition metal oxysalt selected by the plant carbon-supported metal compound nano material provided by the invention can be reduced to generate a new transition metal compound in a high-temperature carbonization process, and the outstanding metal affinity of the transition metal oxysalt enables metal ions to be uniformly deposited in the interior and on the surface of the transition metal compound preferentially, so that the possible growth of metal dendrites is effectively inhibited, and meanwhile, extra capacity is provided.
4. The technical scheme of the invention can realize the regulation and control of the structural morphology of the carbon material and the composition of the carbon material and the metal-philic material through one-step dipping pyrolysis, has simple and efficient operation and strong repeatability, has obvious operation advantages compared with the traditional step-by-step processing method, and can effectively save time cost and economic cost.
Drawings
To further illustrate the embodiments of the present invention, the following are some drawings illustrating embodiments.
FIG. 1 is a scanning electron microscope image of the plant carbon-supported metal compound nanomaterial prepared in example 1 of the present invention.
FIGS. 2 and 3 are XRD patterns of the plant carbon-supported metal compound nano-material prepared in example 1 of the present invention.
Fig. 4 is a raman spectrum of the plant carbon-supported metal compound nanomaterial prepared in example 1 of the present invention.
FIG. 5 is a total spectrum of X-ray photoelectron spectroscopy of the plant carbon-supported metal compound nanomaterial prepared in example 1 of the present invention.
FIG. 6 is a high resolution spectrum of N element in the plant carbon supported metal compound nanomaterial prepared in example 1 of the present invention.
FIG. 7 is a high-resolution spectrum of S element in the plant carbon supported metal compound nanomaterial prepared in example 1 of the present invention.
FIG. 8 is a high-resolution spectrum of Ni element in the plant carbon-supported metal compound nanomaterial prepared in example 1 of the present invention.
Fig. 9 is a coulomb efficiency test chart in a button-type half-cell when the plant carbon-supported metal compound nanomaterial prepared in example 1 of the present invention is used as a sodium metal negative electrode modified material.
Fig. 10 is a graph showing the cycle stability test of the plant carbon-supported metal compound nanomaterial prepared in example 1 of the present invention in a symmetric battery when the nanomaterial is used as a sodium metal battery modification material.
Fig. 11 is a graph showing the rate performance test in the full cell when the plant carbon-supported metal compound nanomaterial prepared in example 1 of the present invention is used as a sodium metal battery modified material.
Fig. 12 is a test chart of cycle performance in a full cell when the plant carbon-supported metal compound nanomaterial prepared in example 1 of the present invention is used as a sodium metal battery modified material.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are conventional reagent products which are commercially available, and manufacturers are not indicated.
Experimental example 1:
a plant carbon-carried metal compound nano material is prepared by the following steps:
5.000g rape pollen, 0.267g nickel sulfate and 30.000g deionized water are respectively weighed. Firstly, mixing nickel sulfate and deionized water in a beaker to prepare a solution, then adding pollen into the solution, and soaking for 3 hours. And transferring the mixed sample to a plastic culture dish, pre-freezing the mixed sample in a freeze dryer for 12 hours, and freeze-drying the mixed sample for 48 hours. Taking out the freeze-dried sample, placing the freeze-dried sample in a porcelain boat, moving the porcelain boat into a tube furnace, heating the porcelain boat to 150 ℃ at a heating rate of 2.5 ℃/min in an argon atmosphere, and then preserving the heat for 30min; then raising the temperature to 600 ℃ at the same heating rate and then preserving the temperature for 1h. And taking out the sample in the porcelain boat when the temperature of the sample is cooled to room temperature. And transferring the product obtained by pyrolysis into a beaker filled with 200ml of deionized water, and stirring for 12 hours at normal temperature. And (3) carrying out suction filtration on the stirred solution, and drying a solid sample obtained by suction filtration in an oven at 80 ℃ for 10 hours to obtain the plant carbon-supported metal compound nano material.
The scanning electron microscope image of the plant carbon-supported metal compound nano material is shown in figure 1, and as shown in figure 1, the pollen carbon material obtained by the method has a regular ellipsoid shape; XRD and Raman characterization are carried out on the plant carbon-supported metal compound nano material, as shown in figures 2 and 3, niO and Ni can be seen by comparing PDF cards 3 S 2 Characteristic peaks of indicating NiSO during pyrolysis 4 In situ hair growing with pollen charcoalOxidation-reduction reaction is generated, and NiSO4 is converted into sodium-philic NiO and Ni 3 S 2 . XPS detection is performed on the plant carbon-supported metal compound nanomaterial to obtain an X-ray photoelectron spectroscopy full spectrum and a target element high-resolution spectrum, as shown in fig. 4 to 8, the plant carbon-supported metal compound nanomaterial comprises nitrogen, sulfur, oxygen and nickel atoms, wherein the nitrogen atom percentage is as follows: 2.51at.%, atomic percent of sulfur: 6.69at.%, atomic percent of oxygen: 12.7at.%, the atomic percent of nickel is: 5.83at.%.
Example 2 (rape pollen is changed to flax)
5.004g of flax, 0.265g of nickel sulfate and 30.003g of deionized water were weighed out respectively. Firstly, mixing nickel sulfate and deionized water in a beaker to prepare a solution, then adding flax into the solution, and soaking for 3 hours. And transferring the mixed sample to a plastic culture dish, pre-freezing the mixed sample in a freeze dryer for 12 hours, and freeze-drying the mixed sample for 48 hours. Taking out the freeze-dried sample, placing the freeze-dried sample in a porcelain boat, moving the porcelain boat into a tube furnace, heating the porcelain boat to 150 ℃ at a heating rate of 2.5 ℃/min in an argon atmosphere, and then preserving the heat for 30min; then the temperature is raised to 600 ℃ at the same heating rate and then is kept for 1h. And taking out the sample in the porcelain boat when the temperature of the sample is cooled to room temperature. And transferring the product obtained by pyrolysis into a beaker filled with 200ml of deionized water, and stirring for 12 hours at normal temperature. And (3) carrying out suction filtration on the stirred solution, and drying a solid sample obtained by suction filtration in an oven at 80 ℃ for 10 hours to obtain the plant carbon-supported metal compound nano material.
Example 3 (rape pollen is replaced by corncob)
5.003g of corncob, 0.266g of nickel sulfate and 30.001g of deionized water were weighed, respectively. Firstly, mixing nickel sulfate and deionized water in a beaker to prepare a solution, then adding corncobs into the solution, and soaking for 3 hours. And transferring the mixed sample to a plastic culture dish, pre-freezing the mixed sample in a freeze dryer for 12 hours, and freeze-drying the mixed sample for 48 hours. Taking out the freeze-dried sample, placing the freeze-dried sample in a porcelain boat, transferring the porcelain boat into a tube furnace, heating to 150 ℃ at a heating rate of 2.5 ℃/min in an argon atmosphere, and then preserving heat for 30min; then raising the temperature to 600 ℃ at the same heating rate and then preserving the temperature for 1h. And taking out the sample in the porcelain boat when the temperature of the sample is cooled to room temperature. And transferring the product obtained by pyrolysis into a beaker filled with 200ml of deionized water, and stirring for 12 hours at normal temperature. And (3) carrying out suction filtration on the stirred solution, and drying a solid sample obtained by suction filtration in an oven at 80 ℃ for 10h to obtain the plant carbon-supported metal compound nano material.
Example 4 (rape pollen is changed to bean root)
5.005g of bean roots, 0.269g of nickel sulfate and 30.004g of deionized water were weighed respectively. Firstly, mixing nickel sulfate and deionized water in a beaker to prepare a solution, then adding the bean roots into the solution, and soaking for 3 hours. And transferring the mixed sample to a plastic culture dish, pre-freezing the mixed sample in a freeze dryer for 12 hours, and freeze-drying the mixed sample for 48 hours. Taking out the freeze-dried sample, placing the freeze-dried sample in a porcelain boat, moving the porcelain boat into a tube furnace, heating the porcelain boat to 150 ℃ at a heating rate of 2.5 ℃ per minute in an argon atmosphere, and then preserving the heat for 30min; then raising the temperature to 600 ℃ at the same temperature raising rate and preserving the temperature for 1h. And taking out the sample in the porcelain boat when the temperature of the sample is cooled to room temperature. And transferring the product obtained by pyrolysis into a beaker filled with 200ml of deionized water, and stirring for 12 hours at normal temperature. And (3) carrying out suction filtration on the stirred solution, and drying a solid sample obtained by suction filtration in an oven at 80 ℃ for 10h to obtain the plant carbon-supported metal compound nano material.
Example 5 (Nickel sulfate instead of cobalt sulfate)
5.001g of rape pollen, 0.266g of cobalt sulfate and 30.001g of deionized water are respectively weighed. Firstly, mixing cobalt sulfate and deionized water in a beaker to prepare a solution, then adding pollen into the solution, and soaking for 3 hours. And transferring the mixed sample to a plastic culture dish, pre-freezing the mixed sample in a freeze dryer for 12 hours, and freeze-drying the mixed sample for 48 hours. Taking out the freeze-dried sample, placing the freeze-dried sample in a porcelain boat, moving the porcelain boat into a tube furnace, heating the porcelain boat to 150 ℃ at a heating rate of 2.5 ℃/min in an argon atmosphere, and then preserving the heat for 30min; then raising the temperature to 600 ℃ at the same heating rate and then preserving the temperature for 1h. And taking out the sample in the porcelain boat when the temperature of the sample is cooled to room temperature. And transferring the product obtained by pyrolysis into a beaker filled with 200ml of deionized water, and stirring for 12 hours at normal temperature. And (3) carrying out suction filtration on the stirred solution, and drying a solid sample obtained by suction filtration in an oven at 80 ℃ for 10h to obtain the plant carbon-supported metal compound nano material.
Example 6 (mass ratio of rape pollen to nickel sulfate was adjusted to 5)
Respectively weighing 5.002g of rape pollen, 1.001g of nickel sulfate and 30.002g of deionized water. Firstly, mixing nickel sulfate and deionized water in a beaker to prepare a solution, then adding pollen into the solution, and soaking for 3 hours. And transferring the mixed sample to a plastic culture dish, pre-freezing the mixed sample in a freeze dryer for 12 hours, and freeze-drying the mixed sample for 48 hours. Taking out the freeze-dried sample, placing the freeze-dried sample in a porcelain boat, transferring the porcelain boat into a tube furnace, heating to 150 ℃ at a heating rate of 2.5 ℃/min in an argon atmosphere, and then preserving heat for 30min; then raising the temperature to 600 ℃ at the same heating rate and then preserving the temperature for 1h. And taking out the sample in the porcelain boat when the temperature of the sample is cooled to room temperature. And transferring the product obtained by pyrolysis into a beaker filled with 200ml of deionized water, and stirring for 12 hours at normal temperature. And (3) carrying out suction filtration on the stirred solution, and drying a solid sample obtained by suction filtration in an oven at 80 ℃ for 10h to obtain the plant carbon-supported metal compound nano material.
Example 7 (concentration of transition Metal oxosalt solution adjusted to 0.005g/cm 3 )
Respectively weighing 5.002g of rape pollen, 0.267g of nickel sulfate and 53.403g of deionized water. Firstly, mixing nickel sulfate and deionized water in a beaker to prepare a solution, then adding pollen into the solution, and soaking for 3 hours. And transferring the mixed sample to a plastic culture dish, pre-freezing the mixed sample in a freeze dryer for 12 hours, and freeze-drying the mixed sample for 48 hours. Taking out the freeze-dried sample, placing the freeze-dried sample in a porcelain boat, moving the porcelain boat into a tube furnace, heating the porcelain boat to 150 ℃ at a heating rate of 2.5 ℃/min in an argon atmosphere, and then preserving the heat for 30min; then raising the temperature to 600 ℃ at the same heating rate and then preserving the temperature for 1h. And taking out the sample in the porcelain boat when the temperature of the sample is cooled to room temperature. And transferring the product obtained by pyrolysis into a beaker filled with 200ml of deionized water, and stirring for 12 hours at normal temperature. And (3) carrying out suction filtration on the stirred solution, and drying a solid sample obtained by suction filtration in an oven at 80 ℃ for 10h to obtain the plant carbon-supported metal compound nano material.
Example 8 (adjustment of drying Process to vacuum drying)
Respectively weighing 5.006g of rape pollen, 0.267g of nickel sulfate and 30.002g of deionized water. Firstly, mixing nickel sulfate and deionized water in a beaker to prepare a solution, then adding pollen into the solution, and soaking for 3 hours. The mixed sample is transferred to a glass watch glass and then placed into a vacuum oven, and the vacuum oven is used for baking for 24 hours at 80 ℃ under a vacuum state. Taking out the dried sample, placing the sample in a porcelain boat, moving the porcelain boat into a tube furnace, heating the porcelain boat to 150 ℃ at a heating rate of 2.5 ℃/min in an argon atmosphere, and then preserving the heat for 30min; then raising the temperature to 600 ℃ at the same heating rate and then preserving the temperature for 1h. And taking out the sample in the porcelain boat when the temperature of the sample is cooled to room temperature. And transferring the product obtained by pyrolysis into a beaker filled with 200ml of deionized water, and stirring for 12 hours at normal temperature. And (3) carrying out suction filtration on the stirred solution, and drying a solid sample obtained by suction filtration in an oven at 80 ℃ for 10 hours to obtain the plant carbon-supported metal compound nano material.
Example 9 (Pre-oxidation temperature adjusted to 250 ℃ C.)
Respectively weighing 5.003g of rape pollen, 0.265g of nickel sulfate and 30.001g of deionized water. Firstly, mixing nickel sulfate and deionized water in a beaker to prepare a solution, then adding pollen into the solution, and soaking for 3 hours. And transferring the mixed sample to a plastic culture dish, pre-freezing the mixed sample in a freeze dryer for 12 hours, and freeze-drying the mixed sample for 48 hours. Taking out the freeze-dried sample, placing the freeze-dried sample in a porcelain boat, moving the porcelain boat into a tube furnace, heating the porcelain boat to 250 ℃ at a heating rate of 2.5 ℃/min in an argon atmosphere, and then preserving the heat for 30min; then raising the temperature to 600 ℃ at the same heating rate and then preserving the temperature for 1h. And taking out the sample in the porcelain boat when the temperature of the sample is cooled to room temperature. And transferring the product obtained by pyrolysis into a beaker filled with 200ml of deionized water, and stirring for 12 hours at normal temperature. And (3) carrying out suction filtration on the stirred solution, and drying a solid sample obtained by suction filtration in an oven at 80 ℃ for 10h to obtain the plant carbon-supported metal compound nano material.
Example 10 (carbonization temperature adjusted to 2000 ℃ C.)
Respectively weighing 5.002g of rape pollen, 0.268g of nickel sulfate and 30.002g of deionized water. Firstly, mixing nickel sulfate and deionized water in a beaker to prepare a solution, then adding pollen into the solution, and soaking for 3 hours. And transferring the mixed sample to a plastic culture dish, pre-freezing the mixed sample in a freeze dryer for 12 hours, and freeze-drying the mixed sample for 48 hours. Taking out the freeze-dried sample, placing the freeze-dried sample in a porcelain boat, moving the porcelain boat into a tube furnace, heating the porcelain boat to 150 ℃ at a heating rate of 2.5 ℃/min in an argon atmosphere, and then preserving the heat for 30min; then raising the temperature to 2000 ℃ at the same temperature raising rate and then preserving the temperature for 1h. And taking out the sample in the porcelain boat when the temperature of the sample is cooled to room temperature. And transferring the product obtained by pyrolysis into a beaker filled with 200ml of deionized water, and stirring for 12 hours at normal temperature. And (3) carrying out suction filtration on the stirred solution, and drying a solid sample obtained by suction filtration in an oven at 80 ℃ for 10h to obtain the plant carbon-supported metal compound nano material.
Example 11 (incubation time adjusted to 3 h)
5.007g of rape pollen, 0.269g of nickel sulfate and 30.001g of deionized water are respectively weighed. Firstly, mixing nickel sulfate and deionized water in a beaker to prepare a solution, then adding pollen into the solution, and soaking for 3 hours. And transferring the mixed sample to a plastic culture dish, pre-freezing the mixed sample in a freeze dryer for 12 hours, and freeze-drying the mixed sample for 48 hours. Taking out the freeze-dried sample, placing the freeze-dried sample in a porcelain boat, transferring the porcelain boat into a tube furnace, heating to 150 ℃ at a heating rate of 2.5 ℃/min in an argon atmosphere, and then preserving heat for 30min; then raising the temperature to 600 ℃ at the same heating rate and then preserving the temperature for 3h. And taking out the sample in the porcelain boat when the temperature of the sample is cooled to room temperature. And transferring the product obtained by pyrolysis into a beaker filled with 200ml of deionized water, and stirring for 12 hours at normal temperature. And (3) carrying out suction filtration on the stirred solution, and drying a solid sample obtained by suction filtration in an oven at 80 ℃ for 10h to obtain the plant carbon-supported metal compound nano material.
Example 12 (immersion time adjusted to 6 h)
Respectively weighing 5.000g of rape pollen, 0.267g of nickel sulfate and 30.005g of deionized water. Firstly, mixing nickel sulfate and deionized water in a beaker to prepare a solution, then adding pollen into the solution, and soaking for 6 hours. And transferring the mixed sample to a plastic culture dish, pre-freezing the mixed sample in a freeze dryer for 12 hours, and freeze-drying the mixed sample for 48 hours. Taking out the freeze-dried sample, placing the freeze-dried sample in a porcelain boat, moving the porcelain boat into a tube furnace, heating the porcelain boat to 150 ℃/min at a heating rate of 2.5 ℃/min in an argon atmosphere, and then preserving the heat for 30min; then raising the temperature to 600 ℃ at the same heating rate and then preserving the temperature for 1h. And taking out the sample in the porcelain boat when the temperature of the sample is cooled to room temperature. And transferring the product obtained by pyrolysis into a beaker filled with 200ml of deionized water, and stirring for 12 hours at normal temperature. And (3) carrying out suction filtration on the stirred solution, and drying a solid sample obtained by suction filtration in an oven at 80 ℃ for 10h to obtain the plant carbon-supported metal compound nano material.
Comparative example 1 (treatment with pure plant, no metal salt)
Respectively weighing 5.000g of rape pollen and 30.002g of deionized water, mixing in a beaker, transferring the mixed sample into a plastic culture dish, pre-freezing in a freeze dryer for 12h, and freeze-drying for 48h. Taking out the freeze-dried sample, placing the freeze-dried sample in a porcelain boat, moving the porcelain boat into a tube furnace, heating the porcelain boat to 150 ℃ at a heating rate of 2.5 ℃/min in an argon atmosphere, and then preserving the heat for 30min; then raising the temperature to 600 ℃ at the same heating rate and then preserving the temperature for 1h. And taking out the sample in the porcelain boat when the temperature of the sample is cooled to room temperature. And transferring the product obtained by pyrolysis into a beaker filled with 200ml of deionized water, and stirring for 12 hours at normal temperature. And (3) carrying out suction filtration on the stirred solution, and drying the solid sample obtained by suction filtration in an oven at 80 ℃ for 10h to obtain the plant carbon material.
SEM and TEM tests are carried out on the plant carbon-supported metal compound nano composite materials prepared in the examples 1 to 12 and the plant carbon material prepared in the comparative example 1, and the test results are shown in the following table 1:
TABLE 1SEM, TEM characterization test results
BET tests were performed on the plant carbon supported metal compound nanomaterials prepared in examples 1 to 12 and the plant carbon material of comparative example 1, and the results are shown in Table 2:
TABLE 2BET test results
XPS spectrogram analysis is carried out on the plant carbon-supported metal compound nano materials prepared in the examples 1 to 12 to obtain the atom percentage of the heteroatom, and the experimental results are shown in the table 3.
TABLE 3 XPS Spectrum analysis results
The plant-based plant carbon-supported metal compound nano materials of examples 1 to 12 and the plant carbon material of comparative example 1 were mixed with a conductive agent and a binder in a mass ratio of 8.
The button-type sodium metal half cell was assembled with the treated sodium sheet of 12mm diameter as the negative electrode and the plant carbon-supported metal compound nanomaterial obtained in example 1 as the positive electrode, and the coulombic efficiency was tested, and the test chart is shown in fig. 9. Two identical half cells of the electrode material obtained in example 1 were taken, sodium of the same capacity was deposited, the cells were disassembled to take out the electrode tabs, and the two electrode tabs were assembled into a symmetrical cell to test the cycle stability, and the test chart is shown in fig. 10. Two identical half cells of the electrode material obtained in example 1 were charged and discharged for 3 times, pre-sodium treated, discharged to 0.01V, and then taken out. The electrode plates are taken out after the battery is disassembled to be used as the cathode of the full battery, NVP is used as the anode, and the full battery is assembled to test the rate capability and the cycle performance, wherein test graphs are shown in FIGS. 11-12.
And carrying out multiplying power and long cycle test on the prepared sodium metal full battery, wherein a voltage window is 2.6-3.8V, and multiplying power test current densities are sequentially selected as follows: 0.2C, 0.5C, 1C, 2C and 5C, and the long-cycle test current density is 1C, and the test results are shown in Table 4.
The electrodes prepared from the plant-based plant carbon-supported metal compound nano materials of examples 2-12 and the plant carbon material of comparative example 1 were assembled with sodium sheets to form button-type sodium metal half cells under the same test conditions as above.
Comparative example 2: the test was carried out using a pure copper foil with a diameter of 14mm as an electrode, assembled with a sodium sheet to form a coin-type sodium metal half cell, under the same test conditions as described above.
Table 4 button type sodium metal full cell multiplying power and long cycle test results
It can be seen that the specific capacity of the battery at 0.2C current density is 90-130mAh g when the plant carbon-supported metal compound nanomaterial prepared in examples 1-12 is used to modify the sodium metal negative electrode -1 When the specific capacity is increased to 5C, the specific capacity still has 35-80mAh g -1 Showing good rate performance. And when the activated product is cycled for 50 circles after long-cycle test, the specific capacity can reach 85-130mAh g -1 The performance is excellent, and the performance is obviously superior to that of the pure plant carbon material in the comparative example 1 and the pure copper foil in the comparative example 2.
When the plant carbon-carried metal compound nano material prepared in the examples 1 to 12 is used as a modified material of a sodium metal battery, the concentration is 1mA cm -2 ，0.5mAh cm -2 Under the test condition of (2), testing the coulomb efficiency in the button-type half cell; will deposit 3mAh cm -2 Sodium electrode as electrode of symmetric cell A symmetric cell was assembled at 1mA cm -2 ，0.5mAh cm -2 Testing the charge and discharge performance under the test condition. The results are shown in Table 5.
Table 5 sodium deposition stripping test results
From the above results, it is evident that the plant-based plant carbon-supported metal compound nanomaterials of examples 1 to 12 are at 1mA cm -2 ，0.5mAh cm -2 Under the condition, the coulombic efficiency of 93.5-99.9% can still be kept after 320 cycles of circulation, the voltage of a symmetrical battery assembled by the material can still be kept in a stable state after 120 hours of circulation, the long-circulation performance is good, and the performance is obviously superior to that of the pure plant carbon material in the comparative example 1 and that of the pure copper foil in the comparative example 2.
The plant-based plant carbon-supported metal compound nanomaterial of examples 1 to 12 was mixed with a conductive agent and a binder in a mass ratio of 8.
The button-type lithium metal half cell was assembled with the treated lithium sheet having a diameter of 14mm as the negative electrode and the plant carbon-supported metal compound nanomaterial obtained in example 1 as the positive electrode, and the coulombic efficiency thereof was tested. Two identical half batteries made of the electrode material obtained in example 1 were taken, lithium with the same capacity was deposited, the batteries were disassembled to take out electrode plates, and the two electrode plates were assembled to a symmetrical battery to test the cycle stability. Two identical half cells of the electrode material obtained in example 1 were charged and discharged for prelithiation 3 times, and then discharged to 0.01V and taken out. And disassembling the battery, taking out the electrode plate as the negative electrode of the full battery, and assembling the full battery to test the rate capability and the cycle performance by taking the lithium iron phosphate as the positive electrode.
Carrying out multiplying power and long cycle test on the prepared sodium metal full battery, wherein a voltage window is 2.7-4.2V, and multiplying power test current densities are sequentially selected as follows: 0.2C, 0.5C, 1C, 2C, 5C, 10C and 20C, and the long-cycle test current density is 1C, and the test results are shown in Table 6.
TABLE 6 TYPED FULL LITHIUM METAL BATTERY COUPLING AND LONG-CYCLE TEST RESULTS
It can be seen that the specific capacity of the battery at 0.2C current density is 100-145 mAh g when the plant carbon-supported metal compound nanomaterial prepared in examples 1-12 is used to modify a lithium metal negative electrode -1 When the specific capacity is increased to 20C, the specific capacity still remains 20-35 mAh g -1 Showing good rate performance. And when the activated product is circulated for 50 circles after long-cycle test, the specific capacity can reach 90-135 mAh g -1 The performance is excellent, and the performance is obviously superior to that of the pure plant carbon material of the comparative example 1 and the pure copper foil of the comparative example 2.
When the plant carbon-carried metal compound nano material prepared in the examples 1 to 12 is used as a modified material of a lithium metal battery, the concentration is 1mA cm -2 ，0.5mAh cm -2 Under the test conditions of (1), testing the coulomb efficiency in the button-type half cell; deposit 3mAh cm -2 Electrode of lithium as electrode of symmetrical cell A symmetrical cell was assembled, 1mA cm -2 ，0.5mAh cm -2 Testing the charging and discharging performance under the test condition. The results are shown in Table 7.
TABLE 7 lithium deposition Peel test results
From the above results, it is apparent that at 1mA cm -2 ，0.5mAh cm -2 Under the condition of (3), the coulombic efficiency of 94.7-99.9% can still be kept after 320 cycles of circulation, the voltage can still be kept in a stable state after the symmetrical battery assembled by the material is circulated for 120 hours, the long-circulation performance is good, and the performance is obviously superior to that of the pure plant carbon material and the couple in comparative example 1Pure copper foil of ratio 2.
The plant-based plant carbon-supported metal compound nanomaterial of examples 1 to 12 was mixed with a conductive agent and a binder in a mass ratio of 8.
The button-type lithium metal half cell was assembled with the treated zinc sheet having a diameter of 10mm as the negative electrode and the plant carbon-supported metal compound nanomaterial obtained in example 1 as the positive electrode, and the coulombic efficiency thereof was tested. Two identical half batteries made of the electrode material obtained in example 1 are taken, zinc with the same capacity is deposited, the batteries are disassembled, electrode plates are taken out, and the two electrode plates are assembled into a symmetrical battery to test the cycling stability. Two identical half cells of the electrode material obtained in example 1 were charged and discharged for 3 times for pre-zinc, and then discharged to 0.01V and taken out. And disassembling the battery, taking out the electrode plate as the negative electrode of the full battery, and assembling the full battery to test the rate capability and the cycle performance by taking manganese dioxide as the positive electrode.
Carrying out multiplying power and long cycle test on the prepared zinc metal full cell, wherein a voltage window is 1.0-3.9V, and multiplying power test current densities are sequentially selected as follows: 0.2C, 0.5C, 1C, 2C and 5C, and the long-cycle test current density is 1C, and the test results are shown in Table 8.
TABLE 8 coin-shaped zinc full-cell multiplying power and long-cycle test results
It can be seen that the specific capacity of the battery at 0.2C current density is 170-195 mAh g when the plant carbon-supported metal compound nanomaterial prepared in examples 1-12 is used to modify the lithium metal negative electrode -1 And when it is increased to 5C, the ratioThe capacity is still 115-155 mAh g -1 Showing good rate performance. And when the activated product is cycled for 50 circles after long-cycle test, the specific capacity can reach 160-185 mAh g -1 The performance is excellent, and the performance is obviously superior to that of the pure plant carbon material in the comparative example 1 and the pure copper foil in the comparative example 2.
When the plant carbon-carried metal compound nano material prepared in the examples 1 to 12 is used as a zinc metal battery modified material, the concentration is 1mA cm -2 ，0.5mAh cm -2 Under the test conditions of (1), testing the coulomb efficiency in the button-type half cell; deposit 3mAh cm -2 Zinc electrode as electrode of symmetrical cell A symmetrical cell was assembled at 1mA cm -2 ，0.5mAh cm -2 Testing the charging and discharging performance under the test condition. The results are shown in Table 9.
TABLE 9 Zinc deposition Peel test results
| Coulomb efficiency% for 320 cycles | Voltage after 120h of cycling | |
| Example 1 | 99.5 | Keep stable |
| Example 2 | 99.8 | Keep stable |
| Example 3 | 99.7 | Keep stable |
| Example 4 | 97.6 | Keep stable |
| Example 5 | 99.2 | Keep stable |
| Example 6 | 93.2 | Keep stable |
| Example 7 | 99.6 | Keep stable |
| Example 8 | 91.5 | Keep stable |
| Example 9 | 98.8 | Keep stable |
| Example 10 | 95.2 | Keep stable |
| Example 11 | 99.5 | Keep stable |
| Example 12 | 99.0 | Keep stable |
| Comparative example 1 | 51.8 | Shake violently |
| Comparative example 2 | 17.7 | Out of range, the test stops |
From the above results, it is apparent that at 1mA cm -2 ，0.5mAh cm -2 Under the condition of (3), the coulombic efficiency of 91.5-99.8% can still be kept after 320 cycles of circulation, the voltage can still be kept in a stable state after the symmetrical battery assembled by the material is circulated for 120 hours, the long circulation performance is good, and the performance is obviously superior to that of the pure plant carbon material in comparative example 1 and the pure copper foil in comparative example 2.
Compared with the electrode material reported at present, the material prepared by the method has more excellent energy storage and quick charge performance.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A plant carbon-supported metal compound nanocomposite, wherein the nanocomposite is uniformly supported with a metal compound, the metal compound comprising: titanium carbide, titanium nitride, titanium oxide, titanium sulfide, vanadium oxide, vanadium sulfide, chromium oxide, chromium sulfide, manganese oxide, iron carbide, iron oxide, iron phosphide, iron sulfide, ferric chloride, cobalt oxide, cobalt phosphide, cobalt sulfide, nickel nitride, nickel oxide, nickel sulfide, copper oxide, copper sulfide, zinc oxide, zinc sulfide, zinc chloride and one or more of same-group metal compounds.
2. The nanocomposite as claimed in claim 1, wherein the structure of the plant carbon supported metal compound nanocomposite is a one-dimensional fiber structure, and the aspect ratio of the material is from 1 to 10000;
or the structure of the plant carbon-supported metal compound nanocomposite is a two-dimensional structure, and the length-width ratio of the material is 1; the thickness range of the material is 0.01-10 μm, and the thickness-to-width ratio is 1;
or the structure of the plant carbon-supported metal compound nanocomposite is a three-dimensional pipeline structure, and the length-diameter ratio of the material is 10; the diameter range is 0.1-10 μm;
or the structure of the plant carbon-supported metal compound nano composite material is a three-dimensional spherical porous structure, and the diameter range of the material is 1-100 mu m.
3. The nanocomposite as claimed in claim 1, wherein the plant carbon supported metal compound nanocomposite has 0.1 to 10at.% of nitrogen;
and/or, the atomic percent of oxygen is 1-15at.%;
and/or, the atomic percentage of sulfur is 1-20at.%;
and/or, the atomic percent of phosphorus is 0.1-10at.%;
and/or the atomic percent of the metal is 1-20at.%.
4. The nanocomposite of claim 1, wherein the plant carbon supported metal compound nanocomposite has a pore size in the range of 0.001 μm to 10 μm;
and/or a pore volume in the range of 0.01cm 3 /g-1cm 3 /g；
And/or a specific surface area of 5m 2 /g-5000m 2 /g。
5. Process for the preparation of a nanocomposite according to any one of claims 1 to 4, characterized in that it comprises the following steps: soaking the plant matter in transition metal oxoacid salt solution, and then sequentially drying, carbonizing, washing and drying the plant matter to obtain the plant carbon-carried metal compound nano material.
6. The method according to claim 5, wherein the precursor of the plant material comprises: at least one of radix Sophorae Tonkinensis, caulis Cannabis, pollen, thallus Porphyrae, populus chinensis, cotton, semen glycines, folium Ginkgo, semen Cucurbitae, and corn cob; the transition metal oxyacid salt includes: at least one of titanium sulfate, manganese sulfate, ferric sulfate, cobalt sulfate, nickel sulfate, copper sulfate, zinc sulfate, chromium nitrate, manganese nitrate, iron nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, copper chlorate, zinc chlorate, vanadium oxalate, an oxyacid salt of an equivalent metal, and the like; the concentration range of the transition metal oxysalt impregnation solution is 0.001g/cm 3 -1 g/cm 3 The mass ratio of the plant material precursor to the transition metal oxysalt is 1-100, and the dipping time is 3-10 h.
7. The preparation method according to claim 5, wherein the drying process conditions before carbonization comprise one or more of normal temperature drying, vacuum drying, heating drying or freeze drying; more preferably, the freeze-drying process conditions include: and transferring the transition metal oxysalt dipping solution to a plastic culture dish, putting the culture dish into a freeze dryer for pre-freezing for 12 hours, and then freeze-drying for 48 hours.
8. The method of claim 5, wherein the carbonizing comprises: heating the dried sample to 100-250 ℃ at a heating rate of 1-20 ℃/min in an inert atmosphere in an argon atmosphere, and then preserving heat for 0.5-2h; then heating to 600-2800 ℃ at the same heating rate, and then preserving heat for 1-3h; and taking out the sample when the temperature of the sample is cooled to room temperature. More preferably, the dried sample is placed in a porcelain boat, the porcelain boat is placed in a tube furnace, the temperature is raised to 150 ℃ at the temperature raising rate of 2.5 ℃/min in the inert atmosphere, and then the temperature is preserved for 30min; then heating to 600 ℃ at the same heating rate, and then preserving heat for 1h; and taking out the sample in the porcelain boat when the temperature of the sample is cooled to room temperature.
9. The method of claim 5, wherein the water washing process comprises: putting the carbonized material into water, uniformly stirring for 8-12h at the rotating speed of 300-500 r/min, and performing suction filtration to obtain a sample for subsequent drying;
and/or the drying treatment temperature is 60-80 ℃, and the drying time is 10-15h.
10. Use of the nanocomposite according to any one of claims 1 to 4 or the plant carbon-supported metal compound nanomaterial prepared by the preparation method according to any one of claims 5 to 9 in a negative electrode of a secondary metal/ion battery.
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| CN116613325A (en) * | 2023-06-14 | 2023-08-18 | 广东格林赛福能源科技有限公司 | Cobalt metal doped rape pollen carbon composite catalyst, preparation method and application thereof |
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