CN117457870A - Vanadium manganese sodium phosphate @ graphene composite material with mesoporous-microporous structure and preparation method and application thereof - Google Patents
Vanadium manganese sodium phosphate @ graphene composite material with mesoporous-microporous structure and preparation method and application thereof Download PDFInfo
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- CN117457870A CN117457870A CN202311442479.XA CN202311442479A CN117457870A CN 117457870 A CN117457870 A CN 117457870A CN 202311442479 A CN202311442479 A CN 202311442479A CN 117457870 A CN117457870 A CN 117457870A
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- Prior art keywords
- vanadium
- sodium
- manganese
- graphene
- phosphate
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 141
- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 112
- ZCZNSUUONOWGBP-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Mn+2].[V+5].[Na+] Chemical compound P(=O)([O-])([O-])[O-].[Mn+2].[V+5].[Na+] ZCZNSUUONOWGBP-UHFFFAOYSA-K 0.000 claims abstract description 76
- 239000011734 sodium Substances 0.000 claims abstract description 43
- 239000011572 manganese Substances 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 239000002105 nanoparticle Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims description 35
- 239000004094 surface-active agent Substances 0.000 claims description 35
- 239000002243 precursor Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052720 vanadium Inorganic materials 0.000 claims description 23
- 229910052708 sodium Inorganic materials 0.000 claims description 22
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 22
- 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 21
- 239000000243 solution Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- 238000001338 self-assembly Methods 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 239000007774 positive electrode material Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- 229910001410 inorganic ion Inorganic materials 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 7
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 7
- 239000001632 sodium acetate Substances 0.000 claims description 7
- 235000017281 sodium acetate Nutrition 0.000 claims description 7
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000006184 cosolvent Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000006012 monoammonium phosphate Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 235000011083 sodium citrates Nutrition 0.000 claims description 4
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- 235000011008 sodium phosphates Nutrition 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 4
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 claims description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 2
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims description 2
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 2
- 229940099594 manganese dioxide Drugs 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
- 229910000016 manganese(II) carbonate Inorganic materials 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
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- OTYNBGDFCPCPOU-UHFFFAOYSA-N phosphane sulfane Chemical compound S.P[H] OTYNBGDFCPCPOU-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 2
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 description 20
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- 229910001415 sodium ion Inorganic materials 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002245 particle Substances 0.000 description 12
- 238000011161 development Methods 0.000 description 11
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 9
- 230000001351 cycling effect Effects 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229910001437 manganese ion Inorganic materials 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 229910001456 vanadium ion Inorganic materials 0.000 description 6
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Provides a vanadium sodium manganese phosphate @ graphene composite material with a mesoporous-microporous structure,the three-dimensional graphene structure comprises a three-dimensional graphene network structure, vanadium manganese sodium phosphate nano particles uniformly dispersed in the three-dimensional graphene network structure and a surface carbon layer coated on the vanadium manganese sodium phosphate nano particles; the molecular formula of the sodium vanadium manganese phosphate is as follows: na (Na) 3+ x Mn x V 2‑x (PO 4 ) 3 Wherein 0 is<x is less than or equal to 1; the thickness of the surface carbon layer is 5-10nm; the mass of the three-dimensional graphene network structure is 2% -15% of the mass of the vanadium manganese sodium phosphate@graphene composite material with the mesoporous-microporous structure; the vanadium manganese sodium phosphate@graphene composite material with a mesoporous-microporous structure is internally provided with a mesoporous-microporous structure.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a vanadium manganese sodium phosphate@graphene composite material with a mesoporous-microporous structure, and a preparation method and application thereof.
Background
Development of renewable clean energy and promotion of energy conversion to green low carbon are necessary routes for achieving 'double carbon' targets and high-quality development of economy and society. However, renewable energy power generation has intermittent and fluctuating characteristics, and is difficult to meet grid connection requirements of a power grid, so that a large-scale energy storage technology becomes a strategic key technology for supporting the development and popularization of renewable energy.
At present, the lithium ion battery technology takes the dominant role in the electrochemical energy storage field, however, 80% of lithium resources in China are imported due to the problems of limited lithium resources, uneven distribution and the like, and in recent years, the development of a power lithium ion battery is likely to cause the lithium ion battery to face the problem of 'neck' of the lithium resources, so that the lithium ion battery cannot meet the large-scale energy storage requirement.
Sodium ion batteries have a similar energy storage mechanism as lithium ion batteries and, more importantly, are rich in sodium resources and low in cost (2022, compared with carbonate, na 2 CO 3 Price of only Li 2 CO 3 And meanwhile, the sodium ion battery has better safety, stability, low-temperature performance and quick charge performance compared with a lithium ion battery due to lower first ionization energy and higher molar conductivity of sodium ions, and is more matched with an energy storage environment. Under the background of the requirement of the development of renewable energy sources for supporting the large-scale energy storage technology, the development of the sodium ion battery energy storage technology has important practical significance and strategic significance.
The development of high performance cathode materials is critical to the development of sodium ion batteries. Na (Na) 3 V 2 (PO 4 ) 3 As a typical NASICON type polyanion compound, the compound has a three-dimensional open framework structure, excellent structural stability and high ionic conductivity, is a sodium ion battery positive electrode material with great development potential, but has lower electricityThe development of the compression platform (about 3.4V), the poor electron conductivity, and the high price and toxicity of the vanadium source limit the development of the compression platform. For example, isomorphous substitution of Mn element for [ VO 6 ]Part of V atoms in the octahedron can obtain a new NASICON material Na 3+x V 2-x Mn x (PO 4 ) 3 (0<x is less than or equal to 1), the material perfectly maintains the three-dimensional framework structure of the NASICON compound, and ensures the rapid ion transmission characteristic; mn can reduce the amount of vanadium at high price and increase the operating voltage (E Mn3+/Mn2+ =3.6v), which is more favorable for improving the energy density of the sodium ion battery; in addition, the manganese element is cheap and easy to obtain, and is green and environment-friendly, so that Na 3+x V 2-x Mn x (PO 4 ) 3 (0<x is less than or equal to 1) is hopeful to become a novel sodium ion battery anode material with high energy density and low cost. On the other hand, na 3+x V 2-x Mn x (PO 4 ) 3 (0<x is less than or equal to 1) and Na 3 V 2 (PO 4 ) 3 As such, there are poor electron conductivity and limited ion diffusion capacity, thereby affecting efficient use of the active material and exertion of rate capability thereof.
Disclosure of Invention
Aiming at the defects of the vanadium manganese phosphate electrode material in the prior art, the first aim of the invention is to provide a vanadium manganese sodium phosphate@graphene composite material (Na 3+x V 2-x Mn x (PO 4 ) 3 (0<x is less than or equal to 1)), the structure is composed of a three-dimensional graphene network structure and carbon-coated vanadium manganese sodium phosphate nano particles inlaid in the three-dimensional network structure, the structure not only ensures uniform carbon coating of the surfaces of primary active particles, but also ensures sufficient contact and electric connection between the active particles, thereby realizing efficient conduction of electrons and ions. The structure can ensure the high-efficiency utilization of each active particle, and can also ensure the structural stability and electrochemical stability of each active particle in the charge and discharge process.
The second object of the invention is to provide a method for preparing the vanadium manganese sodium phosphate@graphene composite material with a mesoporous-microporous structure based on a composite solvent/surfactant synergistic self-assembly method and a solid phase method, wherein the preparation method is based on a solvent and surfactant synergistic self-assembly method and utilizes an organic composite solvent soft template to generate a porous structure in situ. Inorganic ions and graphene in a free state are guided to be orderly and spatially arranged to form a self-assembly body by selectively utilizing non-covalent acting forces such as electrostatic interaction, hydrogen bonds and van der Waals force, so that intermolecular interaction is regulated and controlled in a solvent volatilization process, a vanadium manganese sodium phosphate precursor and graphene form an orderly assembly structure, meanwhile, composite solvents with different boiling points are volatilized successively to generate a porous structure, and finally the porous three-dimensional graphene network embedded vanadium manganese sodium phosphate composite material is formed through high-temperature solid phase reaction. The composite material prepared by the method has good conductivity, high crystallinity and good structural stability, and relatively high-energy-consumption pretreatment processes such as hydrothermal reaction or solvothermal reaction are not needed. The method has the advantages of mild and environment-friendly components, simple operation, low cost and great industrial application prospect.
The third object of the invention is to provide a battery, wherein the sodium ion battery positive electrode material uses the vanadium manganese sodium phosphate@graphene composite material with the mesoporous-microporous structure provided by the first object of the application, and the battery shows excellent sodium storage performance.
According to the technical scheme, the vanadium manganese sodium phosphate@graphene composite material with the mesoporous-microporous structure comprises a three-dimensional graphene network structure, vanadium manganese sodium phosphate nano particles uniformly dispersed in the three-dimensional graphene network structure and a surface carbon layer coated on the vanadium manganese sodium phosphate nano particles; the molecular formula of the sodium vanadium manganese phosphate is as follows: na (Na) 3+x V 2-x Mn x (PO 4 ) 3 Wherein 0 is<x is less than or equal to 1; the thickness of the surface carbon layer is 5-10nm; the mass of the three-dimensional graphene network structure is 2% -15%, preferably 3% -6% of the mass of the vanadium manganese sodium phosphate@graphene composite material with the mesoporous-microporous structure; the vanadium manganese sodium phosphate@graphene composite material with the mesoporous-microporous structure is internally provided with a mesoporous-microporous structure.
The vanadium manganese sodium phosphate@graphene composite material with the mesoporous-microporous structure is formed by uniformly embedding carbon-coated vanadium manganese sodium phosphate nano particles in a porous three-dimensional graphene network structure, so that on one hand, the surface electron conduction of primary active particles is ensured, and on the other hand, the three-dimensional graphene network with the mesoporous-microporous structure ensures the electron transmission and ion diffusion among different carbon-coated vanadium manganese sodium phosphate nano particles, so that a high-efficiency electron and ion conduction system is realized.
The invention also provides a preparation method of the vanadium manganese sodium phosphate@graphene composite material with the mesoporous-microporous structure, which comprises the following steps:
s1, dissolving a vanadium source, a manganese source, a sodium source and a phosphorus source in water to obtain a mixed inorganic ion solution;
s2, dissolving a surfactant in the composite organic solvent, adding graphene to uniformly disperse the surfactant, adding the dispersion liquid into the mixed inorganic ion aqueous solution obtained in the step S1, and stirring to obtain a uniform mixed liquid;
s3, placing the uniform mixed solution obtained in the step S2 into an open system, and evaporating the solvent by controlling the temperature to perform a self-assembly process of graphene, inorganic ions and a surfactant to obtain a vanadium sodium manganese phosphate precursor/surfactant/graphene mixture precursor with a porous structure;
s4, placing the vanadium sodium manganese phosphate precursor/the surfactant/the graphene precursor in a tube furnace and roasting in an inert atmosphere; and after roasting, naturally cooling to room temperature to obtain the vanadium manganese sodium phosphate @ graphene composite material with the mesoporous-microporous structure.
Further, in the step S1: the vanadium source comprises at least one of ammonium metavanadate, sodium metavanadate, vanadium pentoxide, vanadium trioxide, vanadium dioxide, vanadyl sulfate, orthovanadate, vanadium acetylacetonate and vanadium trichloride; the sodium source comprises at least one of sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, sodium phosphate, sodium citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium nitrate and sodium chloride; the manganese source comprises at least one of manganese nitrate, manganese dichloride, manganese carbonate, manganese acetate, manganese dioxide, manganese sulfate and manganese hydroxide; the phosphorus source is at least one of phosphoric acid, monoammonium phosphate, diammonium phosphate, sodium dihydrogen phosphate and ammonium phosphate; the molar ratio of the vanadium element, the sodium element, the manganese element and the phosphorus element in the vanadium source, the sodium source, the manganese source and the phosphorus source is (2-x): (3+x): x:3, wherein x is more than 0 and less than or equal to 1; if the vanadium source is insoluble in water, adding a cosolvent to dissolve the vanadium source, wherein the cosolvent is a medium strong acid; the stirring rate was 200-500rpm.
Further, in the step S1: the vanadium source is at least one of ammonium metavanadate, sodium metavanadate, vanadium pentoxide, orthovanadate and vanadium trichloride; the sodium source is at least one of sodium carbonate, sodium bicarbonate, sodium acetate, sodium phosphate, sodium citrate, sodium dihydrogen phosphate and disodium hydrogen phosphate; the cosolvent is at least one of sulfurous acid, phosphoric acid, oxalic acid and oxalic acid.
Further, in the step S2: the compound organic solvent comprises at least two of acetonitrile, isopropanol, ethylene glycol, methanol, ethanol, tetrahydrofuran, acetone, N' -dimethylformamide and acetic acid; the volume ratio of the composite organic solvent to the water in the step S1 is 1: (0.3-10).
Further, in the step S2, the volume ratio of the compound organic solvent to the water in the step S1 is 1: (0.5-5);
further, in the step S2: the surfactant is at least one of triblock copolymer P123, triblock copolymer F127, polyether, hydroxyethyl cellulose, polyacrylamide, polyvinylpyrrolidone, sodium dodecyl sulfate and polyethylene glycol; the graphene comprises at least one of undoped graphene, oxidized graphene, nitrogen-doped graphene, sulfur-doped graphene, phosphorus-doped graphene, nitrogen-sulfur co-doped graphene and phosphorus-sulfur co-doped graphene; the mass ratio of the graphene to the surfactant is (5-100): 100.
further, in the step S2: the graphene is at least one of undoped graphene, nitrogen-doped graphene and oxidized graphene.
Further, in the step S3, controlling the temperature means controlling the temperature to be within a range of 40 to 80 ℃; in the step S4, the roasting atmosphere is argon or argon-hydrogen mixed gas, the heating rate in the tube furnace is 1-20 ℃/min, the roasting temperature is 550-850 ℃, and the heat preservation time is 4-12 h.
The invention uses a synergistic induction self-assembly process of a composite solvent and a surfactant, selectively utilizes weak intermolecular interactions such as hydrogen bonds, electrostatic interactions, hydrophilic-hydrophobic interactions, van der Waals forces and the like to guide and regulate inorganic ions, the surfactant and graphene in a free state to form a self-assembly body, utilizes liquid drops formed by the composite solvent as soft templates, and further controls the solvent evaporation speed and temperature in the composite solvent evaporation process to regulate (Na) 3+x V 2-x Mn x (PO 4 ) 3 (0<x is less than or equal to 1)) and graphene, thereby generating a precursor with a mesoporous-microporous structure (mesopore-micropore), and finally forming the three-dimensional graphene network embedded vanadium manganese sodium phosphate composite material with micropores/mesopores through high-temperature solid phase reaction. The composite material has excellent electron conduction/ion transmission rate, effectively inhibits structural phase change of the material during deep charging, and has high specific capacity, excellent multiplying power performance and cycle performance.
The invention provides a simple solution self-assembly method based on a composite solvent/surfactant, and a high-temperature solid phase method is combined to prepare the three-dimensional graphene network embedded vanadium manganese sodium phosphate composite material with a mesoporous-microporous structure. According to the method, liquid drops formed by a composite solvent (such as water, acetonitrile, isopropanol, ethylene glycol, methanol, ethanol, tetrahydrofuran, acetone, N' -dimethylformamide, acetic acid and the like) are used as a soft template, a surfactant (such as hydroxyethyl cellulose, polyacrylamide, polyvinylpyrrolidone, polyether, sodium dodecyl sulfate, polyethylene glycol and the like) is used for regulating the surface tension of the solution and providing a carbon source, after graphene and a vanadium sodium phosphate precursor are added, under the auxiliary effect of the surfactant, metal ions (sodium source, manganese source and vanadium source) and a graphene surface are subjected to self-assembly, and the formation of the precursor with a porous structure is realized by realizing controllable volatilization of the solvent at a low temperature (40-80 ℃). The self-assembly process is regulated by regulating factors such as solvent (category, hydrophilic and hydrophobic property, proportion and the like) of a solution system, surfactant (category, concentration and the like) and finally the three-dimensional graphene network embedded vanadium manganese sodium phosphate composite material with mesopores/micropores is formed through high-temperature solid phase reaction. The method only needs to realize the self-assembly process at low temperature (40-80 ℃), does not need to use pretreatment such as hydrothermal reaction or solvothermal reaction, is easy to amplify, and is environment-friendly and low in energy consumption. The prepared composite material is composed of the carbon-coated vanadium manganese sodium phosphate nano particles and a porous three-dimensional graphene network, on one hand, the structure realizes the uniform carbon coating on the surfaces of the vanadium manganese sodium phosphate nano particles and enables the vanadium manganese sodium phosphate nano particles to grow in situ in the three-dimensional graphene network structure, so that the transmission distance of electrons and ions is shortened, the self-agglomeration of active particles is effectively inhibited, on the other hand, the porous three-dimensional through efficient conductive network is provided, the problem of low electron conductivity and the like of the vanadium manganese sodium phosphate is practically overcome, and the three-dimensional conductive network formed in this way ensures the electron conduction between the active materials, and greatly improves the utilization rate of the active materials. More importantly, the three-dimensional structure formed in the method significantly improves the structural stability and electrochemical stability of the electrode material, so that excellent rate performance and cycle performance are shown.
The invention synchronously provides a battery, and the positive electrode material of the battery comprises the vanadium manganese sodium phosphate@graphene composite material with the mesoporous-microporous structure.
Compared with the prior art, the invention has the advantages that:
1. the vanadium manganese phosphate@graphene composite material with a mesoporous-microporous structure provided by the invention is characterized in that carbon-coated vanadium manganese sodium phosphate nano particles are embedded in a porous three-dimensional graphene network structure, and the structure has the following characteristics: the first carbon-coated vanadium manganese sodium phosphate nano particles not only improve the electronic conductivity of primary particles, but also effectively inhibit the high-temperature growth of the particles, thereby being beneficial to realizing high-rate performance; the three-dimensional conductive network provided by the second and three-dimensional graphene network structures not only provides three-dimensional electronic conduction, but also effectively prevents self-agglomeration of carbon-coated vanadium manganese sodium phosphate nano particles, so that each active material can be utilized effectively, and high specific capacity is realized; thirdly, the composite material has a mesoporous-microporous structure, and is beneficial to improving the efficient transmission and ion diffusion of electrolyte. The product structure is also beneficial to buffering structural stress, so that excellent structural stability and electrochemical stability are shown.
2. The preparation method provided by the invention is a simple composite solvent/surfactant synergistic self-assembly method-high-temperature solid phase method. The mesoporous-microporous structure is provided by adopting a composite solvent and a surfactant, and the self-assembly process of inorganic ions and graphene in the solution, namely the inorganic ions and the graphene directly depend on electrostatic interaction, is induced by the cooperation of the solvent (water, ethanol, glycol, tetrahydrofuran and the like) and the surfactant, and meanwhile, the added surfactant assists in promoting the mutual connection of the processes, so that a three-dimensional network structure is formed. Meanwhile, the surfactant also acts as a carbon source, and an in-situ carbon coating is generated in the high-temperature reaction process. On the other hand, the adopted composite solvent serves as a soft template, and a porous structure precursor is generated in the evaporation process by utilizing the boiling point difference of different solvents. Finally, the high-temperature solid phase method promotes one-step realization of high-crystallinity vanadium manganese phosphate nano particles, in-situ carbon coating and porous three-dimensional graphene network.
3. The preparation method disclosed by the invention is simple in preparation process, environment-friendly in preparation process, low in price and easy to obtain raw materials, suitable for large-scale production and extremely good in industrial application prospect.
4. The vanadium sodium manganese phosphate@graphene composite material with a mesoporous-microporous structure provided by the invention is used as a positive electrode material of a sodium ion battery, and has excellent electrochemical performance, and takes x=0.5 as an example, and Na is adopted as an example 3.5 Mn 0.5 V 1.5 (PO 4 ) 3 (0<x is less than or equal to 1) at 0.1C, the discharge specific capacity is up to 120mAh g -1 At 20C, the specific discharge capacity is 72mAh g -1 After 5000 cycles, the capacity retention rate is 89.7%, more importantly, the material shows good low-temperature performance, can still show excellent cycle stability at-20 ℃, and after 500 cycles, the capacity retention rate is as high as 97.7%.
Drawings
These and/or other aspects and advantages of the present invention will become more apparent and more readily appreciated from the following detailed description of the embodiments of the invention, taken in conjunction with the accompanying drawings, wherein:
fig. 1: vanadium manganese sodium phosphate @ graphene composite material (Na) with mesoporous-microporous structure prepared in example 1 of the invention 3.5 V 1.5 Mn 0.5 (PO 4 ) 3 XRD patterns of the materials prepared in HP-NVMP@3DG-1) and comparative examples 1 and 2;
fig. 2: SEM and TEM images of the vanadium manganese sodium phosphate@graphene composite material with a mesoporous-microporous structure, wherein a) is an SEM image; b) Is a TEM image;
fig. 3: gas adsorption (BET) plots for the materials prepared in inventive example 1, comparative example 2, and pore size distribution plots for the materials prepared in example 1; wherein a) is the gas adsorption (BET) diagram of the materials prepared in example 1, comparative example 2; b) Pore size distribution for the material prepared in example 1;
fig. 4: XPS diagram of vanadium manganese sodium phosphate@graphene composite material with mesoporous-microporous structure prepared in embodiment 1 of the invention;
fig. 5: the vanadium manganese sodium phosphate@graphene composite material with a mesoporous-microporous structure prepared in the embodiment 1 of the invention and the materials prepared in the comparative examples 1 and 2 are used for charge-discharge graphs in electrodes;
fig. 6: the vanadium manganese sodium phosphate @ graphene composite material with the mesoporous-microporous structure prepared in the embodiment 1 of the invention and the materials prepared in the comparative examples 1 and 2 are used for rate performance graphs in electrodes;
fig. 7: the vanadium manganese sodium phosphate@graphene composite material with a mesoporous-microporous structure prepared in the embodiment 1 of the invention and the materials prepared in the comparative examples 1 and 2 are used for cyclic performance graphs in electrodes;
fig. 8: the vanadium manganese sodium phosphate @ graphene composite material with the mesoporous-microporous structure prepared in the embodiment 1 of the invention and the materials prepared in the comparative examples 1 and 2 are used for cycle performance diagrams of electrodes at low temperature (-20 ℃).
Fig. 9: the mesoporous-microporous structure prepared in example 2 of the present inventionVanadium manganese sodium phosphate @ graphene composite (Na) 3.3 V 1.7 Mn 0.3 (PO 4 ) 3 HP-NVMP@3DG-2) and (Na) without three-dimensional graphene network structure 3.3 V 1.7 Mn 0.3 (PO 4 ) 3 Nvmp@c-2) charge-discharge curve graph for use in electrode:
fig. 10: the cycling performance diagrams of the vanadium sodium manganese phosphate@graphene composite material (HP-NVMP@3DG-2) with the mesoporous-microporous structure and the three-dimensional graphene network structure-free (NVMP@C-2) prepared in the embodiment 2 of the invention in the electrode are as follows:
fig. 11: vanadium manganese sodium phosphate @ graphene composite material (Na) with mesoporous-microporous structure prepared in embodiment 3 of the invention 4 VMn(PO 4 ) 3 HP-NVMP@3DG-3) and (Na) without three-dimensional graphene network structure 4 VMn(PO 4 ) 3 Nvmp@c-3) charge-discharge curve graph for use in electrode:
fig. 12: the vanadium manganese sodium phosphate@graphene composite material (HP-NVMP@3DG-3) and (NVMP@C-3) with mesoporous-microporous structure prepared in the embodiment 3 of the invention are used for cyclic performance graphs in an electrode:
Detailed Description
For a better understanding of the present invention, reference will be made to the following detailed description of the invention, taken in conjunction with the accompanying drawings and detailed description.
Example 1
S1, according to the mole ratio of sodium ions, manganese ions, vanadium ions and phosphate ions in a sodium source, a manganese source, a vanadium source and a phosphorus source, the mole ratio is 3.5:0.5:1.5:3, 1.5mmol of ammonium metavanadate, 0.5mmol of manganese acetate, 1.75mmol of sodium carbonate and 3mmol of ammonium dihydrogen phosphate are firstly weighed and dissolved in 100mL of water, and stirred until a clear solution is obtained.
S2 0.4g of P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer) was dissolved in 50mL of a mixed solvent of ethanol and acetonitrile (V Ethylene glycol /V Acetonitrile =1:1) and 20mL graphene oxide solution (concentration 1mg mL -1 ) Stirring was carried out at 450rpm for 2 hours to disperse the particles uniformly. Then, the solution is left to evaporate the solvent in an open state at 50 ℃ to lead the process to gradually formThe self-assembly process between the vanadium manganese sodium phosphate precursor, the graphene and the surfactant is carried out, and finally, a solid state vanadium manganese sodium phosphate precursor/surfactant/graphene oxide mixture is obtained; and finally transferring to an oven for drying.
S3, grinding the precursor, and then placing the ground precursor in a tube furnace for roasting in an argon atmosphere; heating to 750 ℃ at a heating rate of 5 ℃/min, preserving heat for 6h, naturally cooling to room temperature after roasting is finished, and obtaining the vanadium manganese sodium phosphate@graphene composite material (Na) with mesoporous/microporous structure 3.5 V 1.5 Mn 0.5 (PO 4 ) 3 ，HP-NVMP@3DG-1)。
The obtained composite material was subjected to XRD, SEM, TEM, BET and XPS tests, and characterization results are shown in FIGS. 1 to 4. As shown in FIG. 1, all diffraction peaks of the vanadium sodium manganese phosphate in the vanadium sodium manganese phosphate @ graphene composite material obtained in the embodiment are highly consistent with those of vanadium sodium manganese phosphate in a hexagonal system and an R3c space group structure, and the diffraction peaks are sharp in shape, high in strength and free of other miscellaneous peaks. As shown in fig. 2a, the composite material obtained in the embodiment is a hierarchical porous vanadium manganese sodium phosphate composite material constructed by a three-dimensional graphene network, wherein active component vanadium manganese sodium phosphate nano particles are highly uniformly dispersed in the three-dimensional graphene network. As shown in fig. 2b, the active component shows clear lattice fringes, indicating that the active material has high lattice stability, which will also contribute to the maintenance of the structural stability of the electrochemical sodium storage. In addition, the surface of the vanadium manganese sodium phosphate particles shows an amorphous carbon layer of 5-10nm, which is beneficial to improving the electron conductivity of the vanadium manganese sodium phosphate positive electrode material, and simultaneously effectively inhibiting the growth of the particles in the high-temperature roasting process. Based on the above excellent structure, HP-NVMP@3DG-1 shows an IV type isotherm and H3 hysteresis loop, which indicates that mesoporous pores exist, and the pore size distribution diagram further indicates that the void and pore size are 4and 10nm. As shown in fig. 4a, the characteristic peaks of Na, mn, O, V, N, C, P and other elements exist in the full spectrum of XPS, and no impurity peak exists, which indicates successful synthesis of the material. FIG. 4b reflects the valence presence morphology of Mn in this material, the fine spectrum of Mn 2p being divided into four characteristic peaks, including Mn 2p3/2 (about 641.5 eV), mn 2p1/2 (653.7 eV) and their satellite peaks, indicating that they are present in the valence form of +2. FIG. 4c shows XPS spectrum of V, peaks divided into V2 p1/2 and V2 p3/2, at 523.8eV and 517.0eV, respectively, indicating that the valence of V in this electrode material is +3. Fig. 4e shows XPS characteristic spectra of C element, and C1 s has characteristic peaks at three positions of 284.8eV, 285.8eV and 288.7eV, which correspond to covalent bond forms of C element of c= C, C-C and O-c=c, respectively. Fig. 4d is a graph of N element, the fine peak of N1 s shows two types of N defects, namely pyridine nitrogen at 398.3eV and pyrrole nitrogen at 400.9eV, which indicate that nitrogen is mainly present in the carbon layer to enhance charge transfer capability, thereby improving electrochemical performance. Fig. 4e shows XPS characteristic spectra of C element, and C1 s has characteristic peaks at three positions of 284.8eV, 285.8eV and 288.7eV, which correspond to covalent bond forms of C element of c= C, C-C and O-c=c, respectively.
Assembling a battery: weighing 0.07g of the composite material obtained in the embodiment, adding 0.02g of conductive agent acetylene black, 0.01g of polyvinylidene fluoride (PVDF) and a proper amount of N-methyl pyrrolidone, stirring into slurry, coating the slurry on an aluminum foil to prepare a positive plate, taking a metal sodium plate as a negative electrode in a vacuum glove box, taking Whatman GF/D as a diaphragm, and 1mol/LNaClO 4 and/PC (5% FEC) as electrolyte, and assembled into CR2032 button cell, and tested for electrochemical performance, and the test results are shown in FIGS. 5-8.
As shown in FIG. 5, in the half cell assembled by using the vanadium manganese sodium phosphate @ graphene composite material with the mesoporous-microporous structure as the positive electrode material, two discharge platforms appear near 3.4V and 3.9V voltages, and the specific discharge capacity at 0.1C current density is 120.5mAh g -1 The discharge specific capacity of the material (NVMP@C-1) without the three-dimensional graphene network serving as a support is obviously higher than that of the material.
As shown in fig. 6, the manganese sodium vanadium phosphate @ graphene composite material with the mesoporous-microporous structure obtained in the embodiment 1 has the rate capability as a positive electrode material, and has specific discharge capacities of 113.4mAh g at current densities of 0.5C,1C,2C,5C,10C,15C and 20C respectively -1 ，107.7mAh g -1 ，103.7mAh g -1 ，96.4mAh g -1 ，88.2mAh g -1 ，81.1mAh g -1 And 73.8mAh g -1 After the current multiplying power returns to 0.5C, the specific discharge capacity can still be restored to 110mAh g -1 The above composition exhibits excellent high rate performance and electrochemical sodium storage reversibility.
As shown in FIG. 7, the cycling performance of the vanadium manganese sodium phosphate @ graphene composite material with the mesoporous-microporous structure obtained in the embodiment 1 as a positive electrode material is that after 500 circles of cycling at a current density of 1C, the specific discharge capacity is 95.8mAh g -1 Far higher than the sample of comparative example 1 (HP-NVMP@C-1:56.1 mAh g) -1 The method comprises the steps of carrying out a first treatment on the surface of the Comparative example 2 sample NVMP@C-1:31mAh g -1 ) The capacity retention was 85.5%, exhibiting excellent cycle stability.
As shown in FIG. 8, the cycling performance graphs of the vanadium sodium manganese phosphate@graphene composite material with the mesoporous-microporous structure prepared in example 1 of the invention at low temperature (-20 ℃) are compared with the samples HP-NVMP@C-1 and NVMP@C-1 of comparative example 1 and 2 without the mesoporous-microporous structure, the samples HP-NVMP@3DG-1 with the mesoporous-microporous structure have the highest specific discharge capacity and the most stable cycling performance at the 1C multiplying power, and the initial specific discharge capacities are 24.9, 40.0 and 89.1mAh g respectively -1 . After 500 cycles, the capacity retention was 82.9%, 91.0% and 97.1%, respectively. The vanadium manganese sodium phosphate@graphene composite material with a mesoporous-microporous structure is shown to have excellent electrochemical performance under a low-temperature condition.
Example 2
S1, according to the mole ratio of sodium ions, manganese ions, vanadium ions and phosphate ions in a sodium source, a manganese source, a vanadium source and a phosphorus source, the mole ratio of the sodium ions, the manganese ions, the vanadium ions and the phosphate ions is 3.3:0.3:1.7:3, firstly, 0.85mmol of vanadium pentoxide, 0.3mmol of manganese nitrate, 3.3mmol of sodium acetate and 3mmol of ammonium dihydrogen phosphate are weighed and dissolved in 100mL of water, and stirred until a clear solution is obtained.
S2, 0.2g of polyvinylpyrrolidone is dissolved in 50mL of a mixed solvent of ethanol and isopropanol (V Ethanol /V Isopropyl alcohol =1:1) and 20mL graphene oxide solution (concentration 1mg mL -1 ) Stirring was carried out at 450rpm for 2 hours to disperse the particles uniformly. Then, the solution is left in an open state to evaporate the solvent in the environment of 40 ℃, and the vanadium manganese sodium phosphate precursor, the graphene and the surfactant which are gradually formed in the process are guidedThe self-assembly process is carried out, and finally, a solid state vanadium sodium manganese phosphate precursor/surfactant/graphene oxide mixture is obtained; and finally transferring to an oven for drying.
S3, grinding the precursor, and then placing the ground precursor in a tube furnace for roasting in an argon atmosphere; heating to 550 ℃ at a heating rate of 5 ℃/min, preserving heat for 8h, and naturally cooling to room temperature after roasting is finished to obtain the vanadium manganese sodium phosphate@graphene composite material (Na) with a mesoporous-microporous structure 3.3 V 1.7 Mn 0.3 (PO 4 ) 3 ，HP-NVMP@3DG-2)。
As shown in FIG. 9, in example 2, the prepared vanadium manganese sodium phosphate @ graphene composite material (HP-NVMP @3 DG-2) with a mesoporous-microporous structure was used as a positive electrode material and a battery was assembled, two discharge platforms were present near 3.4V and 3.9V voltages, and the specific discharge capacity at 0.1C current density was 119.9mAh g -1 Is obviously higher than that of a comparison material without a three-dimensional graphene network structure (Na 3.3 V 1.7 Mn 0.3 (PO 4 ) 3 NVMP@C-2) [ NVMP@C-2 and HP-NVMP@3DG-2 are prepared under the same condition, wherein the step of adding graphene oxide solution into S2 in the preparation process of HP-NVMP@3DG-2 is not needed]Is a specific discharge capacity of (a).
As shown in FIG. 10, the cycling performance of the vanadium manganese sodium phosphate @ graphene composite material with the mesoporous-microporous structure obtained in the embodiment 2 as a positive electrode material is that after 500 circles of cycling at a current density of 1C, the discharge specific capacity is up to 99.8mAh g -1 Is obviously higher than a sample NVMP@C-2 without the three-dimensional porous graphene, and shows excellent cycling stability.
Example 3
S1, according to the mole ratio of sodium ions, manganese ions, vanadium ions and phosphate ions in a sodium source, a manganese source, a vanadium source and a phosphorus source, the mole ratio is 4:1:1:3, firstly, 0.5mmol of vanadium pentoxide, 1mmol of manganese nitrate, 1mmol of sodium acetate and 3mmol of sodium dihydrogen phosphate are weighed and dissolved in 100mL of water, and stirred until a clear solution is obtained.
S2, 0.5g of F127 polypropylene glycol and ethylene oxide addition polymer (polyether) was dissolved in 40mL of a mixed solvent of ethanol and tetrahydrofuran (V Ethanol /V Tetrahydrofuran (THF) =1:1) and adding to the above solutionInto 20mL of graphene oxide solution (concentration 1mg mL) -1 ) Stirring was carried out at 300rpm for 2 hours to disperse the particles uniformly. Then, the solution is subjected to solvent evaporation in an open state at 80 ℃, the self-assembly process between the vanadium manganese sodium phosphate precursor, the graphene and the surfactant, which are gradually formed in the process, is guided, and finally, a solid state vanadium manganese sodium phosphate precursor/surfactant/graphene oxide mixture is obtained; and finally transferring to an oven for drying.
S3, grinding the precursor, and then placing the ground precursor in a tube furnace for roasting in an argon atmosphere; heating to 850 ℃ at a heating rate of 5 ℃/min, preserving heat for 10h, and naturally cooling to room temperature after roasting is finished to obtain the vanadium manganese sodium phosphate@graphene composite material (Na) with a mesoporous-microporous structure 4 VMn(PO 4 ) 3 ，HP-NVMP@3DG-3)。
As shown in FIG. 11, in this example 3, the obtained vanadium manganese sodium phosphate @ graphene composite material HP-NVMP @3DG-3 having a mesoporous-microporous structure was used as a positive electrode material and a battery was assembled, two charge and discharge platforms were present near 3.4V and 3.6V voltages, and the specific discharge capacity at a current density of 0.1C was 97.9mAh g -1 The specific discharge capacity of the porous graphene is 93.9mAh g higher than that of a comparative sample without a three-dimensional porous graphene network as a support -1 。
As shown in fig. 12, the cycling performance of the vanadium manganese sodium phosphate @ graphene composite material with the mesoporous-microporous structure obtained in the present example 3 as a positive electrode material was that after 100 cycles at a current density of 1C, the specific discharge capacity was 94.8mAh g -1 Compared with a comparative sample without a three-dimensional graphene network structure (Na 4 VMn(PO 4 ) 3 NVMP@C-3)) [ NVMP@C-3 and HP-NVMP@3DG-3 were prepared under the same conditions, except that there was no step of adding graphene oxide solution to S2 during the preparation of HP-NVMP@3DG-3]The lifting rate is more than 35 percent.
Comparative example 1
In order to examine the influence of a mesoporous-microporous structure and a graphene network structure on the performance of a vanadium sodium manganese phosphate anode material, a vanadium sodium manganese phosphate @ C composite material (NVMP @ C-1) without the mesoporous-microporous structure and graphene is designed and prepared and used as a comparison material, and the detailed steps are as follows: s1, according to the mole ratio of sodium ions, manganese ions, vanadium ions and phosphate ions in a sodium source, a manganese source, a vanadium source and a phosphorus source, the mole ratio is 3.5:0.5:1.5:3, 1.5mmol of ammonium metavanadate, 0.5mmol of manganese acetate, 1.75mmol of sodium carbonate, 3mmol of monoammonium phosphate and 0.4g of P123 in 100mL of water are first weighed and stirred to a clear solution.
S2, evaporating the solution in an open state at 50 ℃ to finally obtain a solid vanadium manganese sodium phosphate precursor/surfactant mixture. And finally transferring to an oven for drying.
S3, grinding the precursor, and then placing the ground precursor in a tube furnace for roasting in an argon atmosphere; heating to 750 ℃ at a heating rate of 5 ℃/min, preserving heat for 6h, and naturally cooling to room temperature after roasting is finished to obtain the vanadium manganese sodium @ C composite material (NVMP @ C-1).
As shown in FIGS. 5, 6, and 7, NVMP@C-1 exhibited only 86.5mAh g at 0.1C -1 Specific capacity, rate capability 10.5mAh g -1 (20C) And cycle performance (capacity after 500 cycles is only 32.08mAh g) -1 ) Much lower than example 1. The specific capacity of the alloy is only 20.6mAh g after 500 circles of circulation at-20 ℃ under the current density of 1C -1 Much lower than example 1.
Comparative example 2
In order to examine the influence of the three-dimensional graphene structure on the performance of the vanadium manganese sodium phosphate anode material, the vanadium manganese sodium phosphate@C composite material (HP-NVMP@C-1) with a mesoporous-microporous structure is designed and prepared to serve as a comparison material, and the detailed steps are as follows: s1, according to the mole ratio of sodium ions, manganese ions, vanadium ions and phosphate ions in a sodium source, a manganese source, a vanadium source and a phosphorus source, the mole ratio is 3.5:0.5:1.5:3, first, 0.75mmol of vanadium pentoxide, 0.5mmol of manganese acetate, 3.5mmol of sodium acetate, 3mmol of monoammonium phosphate and 0.2g of polyvinylpyrrolidone in 100mL of ethanol/water mixed solvent (1:1) were weighed and stirred to a clear solution.
S2, evaporating the solution to dryness in an open state under the environment of 50 ℃, finally obtaining a solid state vanadium manganese sodium phosphate precursor/surfactant precursor, and finally transferring to a 100 ℃ oven for drying.
S3, grinding the precursor, and then placing the ground precursor in a tube furnace for roasting in an argon atmosphere; heating to 700 ℃ at a heating rate of 5 ℃/min, preserving heat for 8 hours, and naturally cooling to room temperature after roasting is finished to obtain the vanadium manganese sodium @ C composite material (HP-NVMP @ C-1).
As shown in FIGS. 5, 6 and 7, HP-NVMP@C-1 exhibited only 98.0mAh g at 0.1C -1 Specific capacity, rate capability 27.4mAh g -1 (20C) And cycle performance (specific capacity after 500 cycles is only 56.1mAh g) -1 ) Much lower than example 1. The specific capacity of the alloy is only 36.7mAh g after 500 circles of circulation at-20 ℃ under the current density of 1C -1 Much lower than example 1.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. The vanadium manganese sodium phosphate@graphene composite material with a mesoporous-microporous structure is characterized by comprising a three-dimensional graphene network structure, vanadium manganese sodium phosphate nano particles uniformly dispersed in the three-dimensional graphene network structure and a surface carbon layer coated on the vanadium manganese sodium phosphate nano particles;
the molecular formula of the sodium vanadium manganese phosphate is as follows: na (Na) 3+x Mn x V 2-x (PO 4 ) 3 Wherein 0 is<x≤1；
The thickness of the surface carbon layer is 5-10nm;
the mass of the three-dimensional graphene network structure is 2% -15% of the mass of the vanadium manganese sodium phosphate@graphene composite material with a mesoporous-microporous structure;
the vanadium manganese sodium phosphate@graphene composite material with the mesoporous-microporous structure is internally provided with a mesoporous-microporous structure.
2. The preparation method of the vanadium manganese sodium phosphate@graphene composite material with the mesoporous-microporous structure as claimed in claim 1, which is characterized by comprising the following steps:
s1, dissolving a vanadium source, a manganese source, a sodium source and a phosphorus source in water to obtain a mixed inorganic ion solution;
s2, dissolving a surfactant in the composite organic solvent, adding graphene to uniformly disperse the surfactant, adding the dispersion liquid into the mixed inorganic ion aqueous solution obtained in the S1, and stirring to obtain uniform mixed liquid;
s3, placing the uniform mixed solution of the S2 into an open system, and performing self-assembly of graphene, inorganic ions and a surfactant by controlling the temperature to evaporate the solvent to obtain a vanadium sodium manganese phosphate precursor/surfactant/graphene mixture precursor with a porous structure;
s4, placing the vanadium sodium manganese phosphate precursor/the surfactant/the graphene precursor in a tube furnace and roasting in an inert atmosphere; and after roasting, naturally cooling to room temperature to obtain the vanadium manganese sodium phosphate @ graphene composite material with the mesoporous-microporous structure.
3. The method for preparing the vanadium manganese sodium phosphate @ graphene composite material with the mesoporous-microporous structure according to claim 2, wherein in S1:
the vanadium source comprises at least one of ammonium metavanadate, sodium metavanadate, vanadium pentoxide, vanadium trioxide, vanadium dioxide, vanadyl sulfate, orthovanadate, vanadium acetylacetonate and vanadium trichloride;
the sodium source comprises at least one of sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, sodium phosphate, sodium citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium nitrate and sodium chloride;
the manganese source comprises at least one of manganese nitrate, manganese dichloride, manganese carbonate, manganese acetate, manganese dioxide, manganese sulfate and manganese hydroxide;
the phosphorus source is at least one of phosphoric acid, monoammonium phosphate, diammonium phosphate, sodium dihydrogen phosphate and ammonium phosphate;
the molar ratio of the vanadium element, the sodium element, the manganese element and the phosphorus element in the vanadium source, the sodium source, the manganese source and the phosphorus source is (2-x): (3+x): x:3, wherein x is more than 0 and less than or equal to 1;
if the vanadium source is insoluble in water, adding a cosolvent to dissolve the vanadium source, wherein the cosolvent is a medium strong acid;
the stirring rate was 200-500rpm.
4. The method for preparing the vanadium manganese sodium phosphate@graphene composite material with a mesoporous-microporous structure according to claim 3, wherein in the step S1:
the vanadium source is at least one of ammonium metavanadate, sodium metavanadate, vanadium pentoxide, orthovanadate and vanadium trichloride;
the sodium source is at least one of sodium carbonate, sodium bicarbonate, sodium acetate, sodium phosphate, sodium citrate, sodium dihydrogen phosphate and disodium hydrogen phosphate;
the cosolvent is at least one of sulfurous acid, phosphoric acid, oxalic acid and oxalic acid.
5. The method for preparing the vanadium manganese sodium phosphate @ graphene composite material with the mesoporous-microporous structure according to claim 1, wherein in the step S2:
the compound organic solvent comprises at least two of acetonitrile, isopropanol, ethylene glycol, methanol, ethanol, tetrahydrofuran, acetone, N' -dimethylformamide and acetic acid;
the volume ratio of the composite organic solvent to the water in S1 is 1: (0.3-10).
6. The method for preparing the vanadium manganese sodium phosphate@graphene composite material with the mesoporous-microporous structure according to claim 1 or 5, wherein in the step S2, the volume ratio of the composite organic solvent to the water in the step S1 is 1: (0.5-5).
7. The method for preparing the vanadium manganese sodium phosphate @ graphene composite material with the mesoporous-microporous structure according to claim 1, wherein in the step S2:
the surfactant is at least one of triblock copolymer P123, triblock copolymer F127, polyether, hydroxyethyl cellulose, polyacrylamide, polyvinylpyrrolidone, sodium dodecyl sulfate and polyethylene glycol;
the graphene comprises at least one of undoped graphene, oxidized graphene, nitrogen-doped graphene, sulfur-doped graphene, phosphorus-doped graphene, nitrogen-sulfur co-doped graphene and phosphorus-sulfur co-doped graphene;
the mass ratio of the graphene to the surfactant is (5-100): 100.
8. the method for preparing the vanadium manganese sodium phosphate @ graphene composite material with the mesoporous-microporous structure according to claim 1 or 7, wherein in the step S2:
the graphene is at least one of undoped graphene, nitrogen-doped graphene and oxidized graphene.
9. The method for preparing the vanadium manganese sodium phosphate@graphene composite material with a mesoporous-microporous structure according to claim 1, which is characterized in that,
in the step S3, controlling the temperature means controlling the temperature within a range of 40-80 ℃;
in the step S4, the roasting atmosphere is argon or argon-hydrogen mixed gas, the heating rate in the tube furnace is 1-20 ℃/min, the roasting temperature is 550-850 ℃, and the heat preservation time is 4-12 h.
10. A battery, characterized in that the positive electrode material of the battery comprises the vanadium sodium manganese phosphate @ graphene composite material with the mesoporous-microporous structure as claimed in claim 1.
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