CN115472801B - Preparation method and application of hydrogenated titanium dioxide modified core-shell structure carbon coated porous ferroferric oxide and nickel oxide - Google Patents
Preparation method and application of hydrogenated titanium dioxide modified core-shell structure carbon coated porous ferroferric oxide and nickel oxide Download PDFInfo
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 53
- 239000011258 core-shell material Substances 0.000 title claims abstract description 46
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 35
- 229910052799 carbon Inorganic materials 0.000 title claims description 34
- 239000002131 composite material Substances 0.000 claims abstract description 41
- 238000003756 stirring Methods 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 235000019441 ethanol Nutrition 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004202 carbamide Substances 0.000 claims abstract description 6
- 239000008103 glucose Substances 0.000 claims abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000004408 titanium dioxide Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011889 copper foil Substances 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- IYFXESRMJKRSNZ-UHFFFAOYSA-L hydrogen carbonate;nickel(2+) Chemical compound [Ni+2].OC([O-])=O.OC([O-])=O IYFXESRMJKRSNZ-UHFFFAOYSA-L 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229920002535 Polyethylene Glycol 1500 Polymers 0.000 claims description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 2
- 229940032296 ferric chloride Drugs 0.000 claims description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 2
- 229960001781 ferrous sulfate Drugs 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 229940093430 polyethylene glycol 1500 Drugs 0.000 claims description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 2
- 229910013872 LiPF Inorganic materials 0.000 claims 1
- 101150058243 Lipf gene Proteins 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 39
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 11
- 239000002114 nanocomposite Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 229910000314 transition metal oxide Inorganic materials 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 150000003608 titanium Chemical class 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- -1 hydrogenated titanium dioxide modified carbon Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 235000011299 Brassica oleracea var botrytis Nutrition 0.000 description 1
- 240000003259 Brassica oleracea var. botrytis Species 0.000 description 1
- 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 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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Abstract
The invention discloses a preparation method of porous ferroferric oxide and nickel oxide with a hydrogenated titanium dioxide modified core-shell structure, belonging to the technical field of metal nano materials, which comprises the following steps: adding ferric salt, nickel salt, urea, glucose and a surfactant into an alcohol/water system, stirring, clarifying and hydrothermally obtaining a composite material; calcining to obtain a composite material; adding a mixed solution of absolute ethyl alcohol and deionized water, stirring, adding ammonia water, formaldehyde and resorcinol, stirring to obtain a mixed solution, and performing hydrothermal reaction to obtain a composite material; adding the mixture into an absolute ethanol solution, stirring to obtain a mixed solution, adding tetrabutyl titanate, and carrying out water bath to obtain a composite material; adding the mixture into a sodium hydroxide solution, stirring, adding a hydrochloric acid solution, stirring, and filtering to obtain a solid; the core-shell ferroferric oxide/nickel oxide composite material modified by the hydrogenated titanium dioxide is obtained by calcining in a tube furnace, and the prepared composite material has the characteristics of regular shape, good uniformity, high electrochemical performance and the like.
Description
Technical Field
The invention relates to the technical field of binary transition metal nano materials, in particular to a preparation method and application of hydrogenated titanium dioxide modified core-shell ferroferric oxide and nickel oxide.
Background
At present, the transition metal oxide is diversified, and compared with a de-intercalation mechanism of graphite and titanium-based materials, the transition metal oxide-based negative electrode material has higher theoretical specific capacity, and is considered to be an ideal lithium ion battery negative electrode material by researchers. However, due to the defects of the transition metal oxide, such as expansion of the transition metal oxide during lithium ion intercalation during oxidation-reduction, the volume becomes large, and the active material is easily detached from the electrode and pulverized, so that the battery capacity is rapidly attenuated and the cycle stability is deteriorated. Such problems seriously hamper the use of transition metal oxides in lithium ion batteries. Titanium dioxide and carbon-based materials are often used as auxiliary materials to modify the stability of the material surface and to compensate for the properties not possessed by the materials themselves, so that novel nanocomposite materials containing titanium dioxide and carbon-based elements are obtained, and have wide application prospects in the aspects of electronics, batteries, catalysts, biomedicine, electric waves and the like.
However, at present, when a single titanium dioxide or carbon-based material is generally used for coating the transition metal oxide, the conductivity of the titanium dioxide is poor; the single-layer carbon coating cannot effectively inhibit the volume expansion of the F transition metal oxide in the battery cycle process for a long time, and the carbon coating process generally requires a higher temperature and does not meet the green chemical requirements.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a preparation method of hydrogenated titanium dioxide modified core-shell structure carbon coated porous ferroferric oxide and nickel oxide, and the prepared composite material has the characteristics of regular shape, good uniformity, high electrochemical performance and the like.
The purpose of the invention is realized in the following way: carbon-coated porous ferroferric oxide and nickel oxide (H-TiO) with hydrogenated titanium dioxide modified core-shell structure 2 /C/Fe 3 O 4 NiO) comprising the steps of:
s1, adding ferric salt, nickel salt, urea, glucose and a surfactant into an alcohol/water system, stirring to obtain a clear mixed solution A, and then transferring the clear mixed solution A into a reaction kettle for hydrothermal reaction to obtain a ferroferric oxide/nickel bicarbonate composite material;
s2, placing the ferroferric oxide/nickel bicarbonate composite material in a tube furnace to calcine in an oxygen/nitrogen atmosphere to obtain a ferroferric oxide/nickel oxide composite material with a porous structure;
s3, adding the porous ferroferric oxide/nickel oxide composite material into a mixed solution of absolute ethyl alcohol and deionized water, and stirring to uniformly disperse the porous ferroferric oxide/nickel oxide composite material; then adding ammonia water, formaldehyde and resorcinol, and stirring to obtain a mixed solution B;
s4, transferring the mixed solution B into a reaction kettle for hydrothermal reaction to obtain a core-shell structure carbon-coated ferroferric oxide/nickel oxide composite material;
s5, adding the core-shell structure carbon coated ferroferric oxide/nickel oxide composite material into an absolute ethanol solution, stirring to obtain a mixed solution C, then adding tetrabutyl titanate, and stirring in a water bath to obtain a titanium dioxide coated core-shell structure carbon coated ferroferric oxide/nickel oxide composite material;
s6, adding the titanium dioxide coated core-shell structure carbon coated ferroferric oxide/nickel oxide composite material into a sodium hydroxide solution, uniformly stirring, slowly adding a hydrochloric acid solution until no bubbles are generated, stirring, and filtering to obtain a solid D;
and S7, placing the solid D in a tube furnace, and calcining the solid D in an argon hydrogen atmosphere to obtain the hydrogenated titanium dioxide modified core-shell ferroferric oxide/nickel oxide composite material.
As a further limitation of the present invention, the iron salt is ferric chloride, ferric chloride hexahydrate or ferrous sulfate, the nickel salt is nickel chloride, nickel hydroxide, and the surfactant is polyethylene glycol-400, polyethylene glycol-1500 or polyethylene glycol 2000.
As a further limitation of the present invention, the mass ratio of the iron salt, nickel salt, urea, glucose, surfactant is 2:2:8:8:1.
As a further limitation of the invention, the hydrothermal temperature of the hydrothermal reaction in the S1 is 180+/-10 ℃ and the hydrothermal time is 8+/-0.5 h.
As a further limitation of the present invention, the ratio of the flow rate and volume of the oxygen-nitrogen mixture in the S2 tube furnace is 1:5, and the calcination temperature is 2 h before the calcination at 300 ℃ and then 2 h at 500 ℃.
As a further limitation of the invention, the molar ratio of ammonia, formaldehyde and resorcinol to the ferroferric oxide/nickel oxide material in S3 is 0.1:0.1:0.2:2.
As a further limitation of the invention, the hydrothermal temperature of the S4 hydrothermal reaction is 100+/-10 ℃ and the hydrothermal time is 24+/-0.5 h.
As a further limitation of the invention, the volume ratio of the mixed solution C in the step S5 to the tetrabutyl titanate is 25:1, the water bath temperature is 48+/-5 ℃, and the water bath time is 12+/-0.5 h.
As a further limitation of the invention, the ratio of the hydrogen to the argon mixture in the step S7 is 1:19, the calcination temperature is 450+/-5 ℃, and the calcination time is 4+/-0.5 h.
The preparation method comprises the following steps of preparing a hydrogenated titanium dioxide modified core-shell structure carbon coated porous ferroferric oxide and nickel oxide composite material, applying the hydrogenated titanium dioxide modified core-shell structure carbon coated porous ferroferric oxide and nickel oxide composite material to prepare a lithium ion battery negative electrode material, and applying the hydrogenated titanium dioxide modified core-shell structure carbon coated porous ferroferric oxide and nickel oxide composite material to prepare the lithium ion battery negative electrode material:
firstly, preparing a slurry bottle, sequentially adding an N-methyl-2-pyrrolidone organic solvent, polyvinylidene fluoride and conductive carbon black into the slurry bottle, and fully stirring;
then, adding the fully ground composite material into a slurry bottle, stirring, coating the prepared slurry on a copper foil by using a coating machine, and vacuum drying the copper foil;
then, cutting the copper foil into electrode slices with the size of coins, and weighing to obtain the mass of active substances on a single electrode;
finally, CR2032 type button cell was mounted in the order of assembly of button cells in an argon-filled glove box, with electrolyte using 1M LiPF 6 The mixture was left to stand 24 and h, followed by a corresponding test.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares a core-shell structure with ferroferric oxide/nickel oxide as a core and a carbon-based material as a shell layer, and utilizes the expansion stability of titanium dioxide to modify the carbon-coated ferroferric oxide/nickel oxide nano material with the core-shell structure. The carbon coating structure can relieve the volume expansion of transition metal oxides such as ferroferric oxide, nickel oxide and the like in the circulating process, and improve the circulating stability of the electrode material. And then, the hydrogenated titanium dioxide is adopted to modify the ferroferric oxide/nickel oxide coated by the carbon-based material, so that the conductivity of the titanium dioxide is greatly improved by hydrogenation treatment, and the rate capability of the electrode material is improved. Meanwhile, the hydrogenated titanium dioxide modifies the ferroferric oxide/nickel oxide composite electrode material coated by the carbon-based material, inhibits the breakage of a carbon layer, relieves the volume expansion and crushing of the ferroferric oxide and nickel oxide nano material in the battery cycle process, and improves the cycle performance of the battery and the cycle performance under high multiplying power; the preparation process is easy to control, simple in process and low in cost, and is suitable for industrial mass production; the prepared hydrogenated titanium dioxide modified carbon-coated core-shell structure ferroferric oxide/nickel oxide nanocomposite has the characteristics of regular morphology, good uniformity and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 shows Fe in the present invention 3 O 4 /Ni(CHO 3 ) 2 Is an X-ray diffraction pattern of (2).
FIG. 2 shows porous Fe in the present invention 3 O 4 X-ray diffraction pattern of NiO.
FIG. 3 shows a porous Fe with a carbon-coated core-shell structure according to the present invention 3 O 4 X-ray diffraction pattern of NiO.
FIG. 4 shows H-TiO according to the invention 2 /C/Fe 3 O 4 X-ray diffraction pattern of NiO.
FIG. 5 is a diagram of Fe in the present invention 3 O 4 /Ni(CHO 3 ) 2 SEM images of (a).
FIG. 6 shows porous Fe in the present invention 3 O 4 SEM image of NiO.
FIG. 7 shows a porous Fe with a carbon-coated core-shell structure according to the present invention 3 O 4 SEM image of NiO。
FIG. 8 is a schematic diagram of H-TiO according to the invention 2 /C/Fe 3 O 4 SEM image of NiO.
FIG. 9 is a schematic diagram of H-TiO according to the present invention 2 /C/Fe 3 O 4 NiO has a current density of 0.3 Ag when used as an anode material of a half-cell button type lithium ion battery -1 Is a cycle performance chart of (c).
FIG. 10 shows H-TiO according to the invention 2 /C/Fe 3 O 4 NiO has a current density of 1 Ag when used as an anode material of a half-cell button type lithium ion battery -1 Is a cycle performance chart of (c).
FIG. 11 is a schematic diagram of H-TiO according to the invention 2 /C/Fe 3 O 4 NiO is used as the anode material of the button-type lithium ion battery of the half cell.
Fig. 12 is an SEM image of hydrogenated titanium dioxide modified core-shell structure ferroferric oxide and nickel oxide according to example 2 of the present invention.
Fig. 13 is an SEM image of hydrogenated titanium dioxide modified core-shell structure ferroferric oxide and nickel oxide according to example 3 of the present invention.
Fig. 14 is an SEM image of hydrogenated titanium dioxide modified core-shell structure ferroferric oxide and nickel oxide according to example 4 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
a preparation method of porous ferroferric oxide and nickel oxide with a hydrogenated titanium dioxide modified core-shell structure comprises the following steps.
S1, adding 2g of ferric trichloride, 2g of nickel chloride, 8 g of urea, 8 g of glucose and 1 g of polyethylene glycol 2000 into a mixed solution of 90 mL deionized water and absolute ethyl alcohol (45 mL:45 mL), stirring 4 h,obtaining a mixed solution A; carrying out hydrothermal reaction on the solution A at 180+/-10 ℃ for 8+/-0.5 h, filtering, centrifugally cleaning a filter cake by water and ethanol respectively, and drying the filter cake to obtain a nano composite material of ferroferric oxide and nickel bicarbonate, namely Fe 3 O 4 /Ni(CHO 3 ) 2 The X-ray diffraction pattern is shown in FIG. 1, and the SEM pattern is shown in FIG. 5.
S2, fe 3 O 4 /Ni(CHO 3 ) 2 Placing the materials in a tube furnace, wherein the atmosphere is oxygen-nitrogen mixed gas, the oxygen flow rate is 1L/h, the nitrogen flow rate is 5L/h, the calcining temperature is 300 ℃, the calcining temperature is 2 h, then the calcining temperature is 500 ℃, the calcining temperature is 2 h, the nano composite material of porous ferric oxide and nickel oxide is obtained, the nano composite material is marked as A-Fe3O4, the X-ray diffraction diagram is shown in figure 2, and the SEM diagram is shown in figure 6.
S3 Fe of 1.6 g 3 O 4 Adding NiO into a mixed solution of 90 mL deionized water and absolute ethyl alcohol (45 mL:45 mL), and magnetically stirring for 60 min; subsequently, 0.9ml of 28% aqueous ammonia, 6 mL formaldehyde and 44 mg resorcinol were added thereto, and 2 h was stirred to obtain a mixed solution B.
S4, carrying out hydrothermal reaction on the mixed solution B at 100+/-10 ℃ for 24+/-0.5 h, filtering, centrifugally cleaning a filter cake by water and ethanol respectively, and drying the filter cake to obtain the carbon-coated core-shell structure Fe 3 O 4 NiO nanocomposite, designated C/Fe 3 O 4 NiO has an X-ray diffraction pattern shown in FIG. 3 and an SEM pattern shown in FIG. 7.
S5, C/Fe 3 O 4 Adding NiO into the absolute ethanol solution of 100 mL, and stirring to obtain a mixed solution C; adding 4 mL tetrabutyl titanate into the mixed solution C, stirring for 12 h at a water bath temperature of 48 ℃, filtering, centrifugally cleaning a filter cake with water and ethanol respectively, and drying the filter cake to obtain a titanium dioxide modified carbon-coated core-shell structure ferroferric oxide sodium/nickel oxide composite material which is recorded as TiO 2 /C/Fe 3 O 4 /NiO。
S6, tiO 2 /C/Fe 3 O 4 Adding NiO into the 1M sodium hydroxide solution of 250 mL, stirring uniformly, slowly adding the 0.1M hydrochloric acid solution until no bubbles are generated,filtering, centrifugally cleaning the filter cake with water and ethanol respectively, and then drying the filter cake to obtain a solid D.
S7, placing the solid D in a tube furnace, calcining by using hydrogen argon atmosphere (volume ratio is 1:19), wherein the calcining temperature is 450+/-5 ℃, and the calcining time is 4+/-0.5H, so as to obtain the hydrogenated titanium dioxide and carbon double-layer coated core-shell ferroferric oxide nano particles, which are marked as H-TiO 2 /C/Fe 3 O 4 The X-ray diffraction pattern is shown in FIG. 4, and the SEM pattern is shown in FIG. 8.
Referring to FIG. 1 as Fe 3 O 4 /Ni(CHO 3 ) 2 X-ray diffraction pattern of (2) confirmed that case 1 successfully produced Fe 3 O 4 /Ni(CHO 3 ) 2 Is a composite material of (a).
FIG. 2 shows Fe 3 O 4 X-ray diffraction pattern of NiO, confirmed that case 1 successfully produced Fe 3 O 4 Composite material of NiO.
FIG. 3 shows porous Fe with carbon-coated core-shell structure 3 O 4 X-ray diffraction pattern of NiO, confirmed that case 1 successfully produced C/Fe 3 O 4 Composite material of NiO.
FIG. 4 shows porous Fe with hydrogenated titanium dioxide modified carbon-coated core-shell structure 3 O 4 X-ray diffraction pattern of NiO, confirmed that case 1 successfully produced H-TiO 2 /C/Fe 3 O 4 Composite material of NiO.
FIG. 5 is a view of Fe 3 O 4 /Ni(CHO 3 ) 2 From the SEM image of (C), fe can be seen 3 O 4 With Ni (CHO) 3 ) 2 The composite material of (2) is in a cauliflower type structure formed by sheets, the thickness of the sheets is about 15 nm, the width is about 200 nm, and the appearance is regular.
FIG. 6 shows porous Fe 3 O 4 SEM image of NiO, from which porous Fe can be seen 3 O 4 The composite material of/Ni is mainly granular, the particle diameter is about 20 and nm, and the irregular sheet structure is accompanied.
FIG. 7 is C/Fe 3 O 4 SEM image of NiO, from which it can be seen that the carbon-based material will be porous Fe 3 O 4 NiO is packed in a spherical form, the diameter of the sphere is about 500 to nm, and a small amount of porous Fe 3 O 4 The NiO nanomaterial was not encapsulated.
FIG. 8 shows H-TiO 2 /C/Fe 3 O 4 SEM of NiO, from which H-TiO can be seen 2 C/Fe 3 O 4 NiO is modified into an irregular block structure, the overall diameter is about 1.5 and um, and the surface of NiO presents a multi-channel gully shape.
Example 2
The H-TiO prepared by the application of porous ferroferric oxide and nickel oxide with hydrogenated titanium dioxide modified core-shell structure 2 /C/Fe 3 O 4 NiO is used as a button type lithium ion cathode material of a half cell, and the preparation process comprises the following steps:
firstly, preparing 1 slurry bottle, sequentially adding 1 mL N-methyl-2-pyrrolidone (NMP) organic solvent, 20 mg polyvinylidene fluoride and 20 mg conductive carbon black into the slurry bottle, and fully stirring for about 20 min;
160 mg active substance H-TiO, which is then thoroughly ground 2 /C/Fe 3 O 4 Adding NiO into a slurry bottle, stirring for 24 and h, respectively coating the prepared slurry on copper foil with the thickness of 30 and mm by using a coating machine, and vacuum drying the copper foil for 8 and h;
then, cutting the copper foil into electrode slices with the size of coins, and weighing to obtain the mass of active substances on a single electrode;
finally, CR2032 type button cell was mounted in the order of assembly of button cells in an argon-filled glove box, with electrolyte using 1M LiPF 6 The mixture was left to stand 24 and h, followed by a corresponding test.
The testing method comprises the following steps: a Xinwei CT-4008 battery tester is used, the voltage range is 0.01-3.00V, and the current density is 0.3 Ag -1 Performing electrochemical performance test; as can be seen from FIGS. 9-11, H-TiO 2 /C/Fe 3 O 4 NiO is used as a cathode material of the lithium ion half battery, and 0.3A g of NiO is used as a cathode material of the lithium ion half battery -1 Has a capacity of 887 mAh g after 200 circles of current density circulation -1 At 1A g -1 After 1000 cycles of current density cycle422 mAh g -1 The rate capability is superior, which indicates that the hydrogenated titanium dioxide modification and the carbon coating structure effectively inhibit the volume expansion of the transition metal oxide in the battery cycle process, and improve the capacity performance.
Example 3:
the procedure of example 1 was followed except that the ferric trichloride of example 1, 4 g, was replaced with 3.8 g ferric trichloride hexahydrate, and the hydrogenated titanium dioxide-modified core-shell ferroferric oxide and nickel oxide nanocomposite was prepared.
Example 4:
the iron trichloride of example 1, 4 g, was replaced with 3.6: 3.6 g ferrous sulfate, and the remainder was the same as in example 1 to produce a hydrogenated titanium dioxide-modified core-shell ferroferric oxide and nickel oxide nanocomposite.
Example 5:
the iron trichloride of example 1, 4 g, was replaced with 3.6. 3.6 g nickel hydroxide, and the rest was the same as in example 1 to prepare a hydrogenated titanium dioxide-modified core-shell ferroferric oxide-nickel oxide nanocomposite.
Fig. 12, 13 and 14 are SEM images of the nanoparticles of example 3, example 4 and example 5, respectively, each of which produced a nanocomposite of hydrogenated titanium dioxide-modified core-shell ferroferric oxide and nickel oxide.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (6)
1. The preparation method of the hydrogenated titanium dioxide modified core-shell structure carbon coated porous ferroferric oxide and nickel oxide is characterized by comprising the following steps of:
s1, adding ferric salt, nickel salt, urea, glucose and a surfactant into an alcohol/water system, stirring to obtain a clear mixed solution A, then transferring into a reaction kettle, and performing hydrothermal reaction to obtain a ferric oxide/nickel bicarbonate composite material, wherein the ferric salt is ferric chloride, ferric chloride hexahydrate or ferrous sulfate, the nickel salt is nickel chloride and nickel hydroxide, the surfactant is polyethylene glycol-400, polyethylene glycol-1500 or polyethylene glycol 2000, the mass ratio of the ferric salt to the nickel salt to the urea to the glucose to the surfactant is 2:2:8:8:1, and the hydrothermal temperature of the hydrothermal reaction in S1 is 180+/-10 ℃ and the hydrothermal time is 8+/-0.5 h;
s2, placing the ferroferric oxide/nickel bicarbonate composite material in a tube furnace to calcine in an oxygen/nitrogen atmosphere to obtain the ferroferric oxide/nickel oxide composite material with a porous structure, wherein the flow rate volume ratio of oxygen and nitrogen mixed gas in the S2 tube furnace is 1:5, the calcination temperature is 2 h before calcination at 300 ℃, and then 2 h is calcined at 500 ℃;
s3, adding the porous ferroferric oxide/nickel oxide composite material into a mixed solution of absolute ethyl alcohol and deionized water, and stirring to uniformly disperse the porous ferroferric oxide/nickel oxide composite material; then adding ammonia water, formaldehyde and resorcinol, and stirring to obtain a mixed solution B;
s4, transferring the mixed solution B into a reaction kettle for hydrothermal reaction to obtain a core-shell structure carbon-coated ferroferric oxide/nickel oxide composite material;
s5, adding the core-shell structure carbon coated ferroferric oxide/nickel oxide composite material into an absolute ethanol solution, stirring to obtain a mixed solution C, then adding tetrabutyl titanate, and stirring in a water bath to obtain a titanium dioxide coated core-shell structure carbon coated ferroferric oxide/nickel oxide composite material;
s6, adding the titanium dioxide coated core-shell structure carbon coated ferroferric oxide/nickel oxide composite material into a sodium hydroxide solution, uniformly stirring, slowly adding a hydrochloric acid solution until no bubbles are generated, stirring, and filtering to obtain a solid D;
and S7, placing the solid D in a tube furnace, and calcining the solid D in an argon hydrogen atmosphere to obtain the hydrogenated titanium dioxide modified core-shell ferroferric oxide/nickel oxide composite material.
2. The method for preparing the hydrogenated titanium dioxide modified core-shell structured carbon coated porous ferroferric oxide and nickel oxide according to claim 1, wherein the molar ratio of ammonia water, formaldehyde and resorcinol to the ferroferric oxide/nickel oxide material in the S3 is 0.1:0.1:0.2:2.
3. The method for preparing the hydrogenated titanium dioxide modified core-shell structure carbon coated porous ferroferric oxide and nickel oxide according to claim 1, wherein the hydrothermal temperature of the S4 hydrothermal reaction is 100+/-10 ℃ and the hydrothermal time is 24+/-0.5 h.
4. The method for preparing the hydrogenated titanium dioxide modified core-shell structured carbon coated porous ferroferric oxide and nickel oxide according to claim 1, wherein the volume ratio of the mixed solution C in the step S5 to the tetrabutyl titanate is 25:1, the water bath temperature is 48+/-5 ℃, and the water bath time is 12+/-0.5 h.
5. The method for preparing the hydrogenated titanium dioxide modified core-shell structured carbon coated porous ferroferric oxide and nickel oxide according to claim 1, wherein the ratio of the hydrogen-argon mixture gas in the step S7 is 1:19, the calcination temperature is 450+/-5 ℃, and the calcination time is 4+/-0.5 h.
6. The application of the hydrogenated titanium dioxide modified core-shell structure carbon coated porous ferroferric oxide and nickel oxide is characterized in that the hydrogenated titanium dioxide modified core-shell structure carbon coated porous ferroferric oxide and nickel oxide composite material prepared by any one of claims 1-5 is applied to the preparation of a lithium ion battery anode material, and the preparation process is as follows:
firstly, preparing a slurry bottle, sequentially adding an N-methyl-2-pyrrolidone organic solvent, polyvinylidene fluoride and conductive carbon black into the slurry bottle, and fully stirring;
then, adding the fully ground composite material into a slurry bottle, stirring, coating the prepared slurry on a copper foil by using a coating machine, and vacuum drying the copper foil;
then, cutting the copper foil into electrode slices with the size of coins, and weighing to obtain the mass of active substances on a single electrode;
finally, in the glove filled with argonCR2032 button cell was mounted in the case in the order of assembly of button cells, wherein 1M LiPF was used as electrolyte 6 The mixture was left to stand 24 and h, followed by a corresponding test.
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