CN109052491A - A kind of preparation method of the porous high entropy oxide material of lithium ion battery negative material spinel-type - Google Patents
A kind of preparation method of the porous high entropy oxide material of lithium ion battery negative material spinel-type Download PDFInfo
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- CN109052491A CN109052491A CN201810815319.8A CN201810815319A CN109052491A CN 109052491 A CN109052491 A CN 109052491A CN 201810815319 A CN201810815319 A CN 201810815319A CN 109052491 A CN109052491 A CN 109052491A
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- high entropy
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- 239000000463 material Substances 0.000 title claims abstract description 46
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000446 fuel Substances 0.000 claims abstract description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002485 combustion reaction Methods 0.000 claims abstract description 11
- 239000002671 adjuvant Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 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 5
- 239000008103 glucose Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011975 tartaric acid Substances 0.000 claims abstract description 4
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 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 3
- 229960001484 edetic acid Drugs 0.000 claims abstract description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000035935 pregnancy Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 11
- 239000000843 powder Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005049 combustion synthesis Methods 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 2
- 229910001960 metal nitrate Inorganic materials 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 150000003624 transition metals Chemical class 0.000 abstract 1
- 235000002639 sodium chloride Nutrition 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005551 mechanical alloying Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- H01M2004/027—Negative electrodes
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Abstract
The invention discloses a kind of preparation methods of the porous high entropy oxide material of lithium ion battery negative material spinel-type, belong to inorganic oxide powder Material Field.This method is low-temperature combustion synthesis, specifically: using metal nitrate for source metal, one or more of tartaric acid, citric acid, glucose, pregnancy urotropine and ethylenediamine tetra-acetic acid mixture is fuel, the characteristics such as granularity and pattern for regulating and controlling the high entropy nm-class oxide powder of spinel-type transition metal by controlling concentration, the type of fuel and additional amount, the type of combustion adjuvant and additional amount and the sparking mode of metal salt raw material.The present invention uses liquid phase ingredient, it is ensured that raw material reaches molecular level mixing, and product realizes stoichiometric ratio；Simultaneously energy saving, high production efficiency, it is environmentally protective, without complicated post-processing the advantages that, and prepare high entropy oxide powder purity is high, granularity is tiny, is evenly distributed and initial discharge capacity with higher and preferable cycle performance.
Description
Technical field
The invention belongs to inorganic oxide powder Material Field, in particular to a kind of lithium ion battery negative material, specifically
Have spinel-type porous (CoCrCuFeNi) for one kind3O4High entropy oxide micrometer/nanometer material and preparation method thereof.
Background technique
Lithium ion battery has that energy density is high, cycle performance is good, self-discharge rate is small, memory-less effect and environmentally protective
Etc. characteristics, in modern mobile electronic device, such as mobile phone, laptop portable electronic product and new-energy automobile
Equal fields show extremely bright application prospect.Negative electrode material is improving battery as one of big composition material of lithium battery four
Capacity and cycle performance in terms of play important function, the core link in lithium battery industry middle reaches.It is negative in lithium ion
In the material of pole, graphite-like carbon negative pole material occupies always leading position because from a wealth of sources, cheap.But one side stone
Black base negative electrode material theoretical specific capacity is low, only 372mAhg-1；Although on the other hand its biggish layer structure is the storage of lithium
Place is provided, but is unfavorable for battery and relevant apparatus and develops to miniaturization；The intercalation potential of graphite-based cathode connects simultaneously
The current potential of nearly lithium metal, is unfavorable for the safety of battery.
Compound transition metal oxide is due to initial capacity with higher and good chemical property and cheaper
Cost the advantages that and be concerned.High entropy oxide material is a kind of novel ceramic to grow up on the basis of high-entropy alloy
Ceramic material is proposed the concept of this new ceramic material of high entropy oxide by the Christina M.Rost in the U.S. first.At present
Research about high entropy oxide material mainly has: Christina M.Rost is prepared using mechanical alloying and solid sintering technology
NaCl type (MgCoNiCuZn) O high entropy oxide block materials (C.M.Rost, E.Sachet, T.Borman,
A.Moballegh, E.C.Dickey, D.Hou, J.L.Jones, S.Curtarolo, J.-P.Maria, Entropy-
Stabilized oxides, Nature Communications, 6 (2015) 8485).A.Sarkar of Germany et al. is using warm
Solution spray-on process, flame spray pyrolysis process and reversed coprecipitation are prepared for NaCl type (MgCoNiCuZn) O high entropy oxidate powder
Body material (A.Sarkar, R.Djenadic, N.J.Usharani, K.P.Sanghvi, V.S.K.Chakravadhanula,
A.S.Gandhi, H.Hahn, S.S.Bhattacharya, Nanocrystalline multicomponent entropy
Stabilised transition metal oxides, Journal of the European Ceramic Society, 37
(2017)747-754.).David et al. has studied Li on this basis+And Ga3+Doping to NaCl type (MgCoNiCuZn) O
Influence (B.David, F.Sylvain, D.Diana, M.A.Kumar, D.Nita, the Colossal of high entropy oxide dielectric constant
Dielectric constant in high entropy oxides, physica status solidi (RRL)-Rapid
Research Letters, 10 (2016) 328-333.).In addition to this, French Dabrowa et al. uses hot isostatic pressing for the first time
Technology is prepared for (CoCrFeMnNi) with spinel structure2O3High entropy oxide block materials (J.
M.Stygar, A.A.Knapik, K.Mroczka, W.Tejchman, M.Danielewski, M.Martin,
Synthesis and microstructure of the(CoCrFeMnNi)3O4high entropy oxide
Characterized by spinel structure, Materials Letters, 216 (2018) 32-36.).Jiang etc.
Using mechanical alloying and solid sintering technology be prepared for perovskite structure the high entropy oxide block materials of series (S.Jiang,
T.Hu, J.Gild, N.Zhou, J.Nie, M.Qin, T.Harrington, K.Vecchio, J.Luo, A new class of
High-entropy perovskite oxides, Scripta Materialia, 142 (2018) 116-120.).Chinese patent
It number proposes to be prepared for for lithium ion battery negative material using the laser molecular beam epitaxy precipitation method for 201711421445.7
(MgCoNiCuZn) O high entropy oxide film material.Not yet retrieve spinel-type (CoCrCuFeNi) at present3O4High entropy oxidation
The relevant report of object material.
Summary of the invention
In order to overcome the deficiencies of the prior art, the technical problem to be solved by the present invention is to design a kind of novel lithium-ion electric
Pond negative electrode material spinel-type (CoCrCuFeNi)3O4High entropy oxide material, while overcoming the prior art, such as mechanical alloying
Method and pyrolysis spray-on process prepare the deficiency of high entropy oxide powder material, and providing one kind, low energy consumption, high production efficiency, green ring
It protects, preparation method of the product without the porous high entropy oxide material of spinel-type of complicated post-processing.
It is porous (CoCrCuFeNi) that the present invention provides a kind of lithium ion battery negative material spinel-type3O4High entropy oxide
The preparation method of material, specifically comprises the following steps:
(1) nitrate for weighing Co, Cr, Cu, Fe and Ni of equimolar amounts, is dissolved in a certain amount of distilled water or ethyl alcohol is water-soluble
It in liquid, stirs evenly, obtains the mixed solution containing metal salt.Wherein in ethanol water volume fraction of ethanol be 20~
80%.
(2) mixture of a certain amount of fuel or fuel and combustion adjuvant is weighed in above-mentioned mixed solution, is stirred evenly simultaneously
The pH that appropriate ammonium hydroxide adjusts mixed solution is added, obtains transparent colloidal sol, in which: the pH range of the solution is adjusted to 6~8,
The molar ratio of the fuel and nitrate metal ion is 1~2: 1；In the mixture of the fuel and combustion adjuvant: combustion adjuvant institute
Accounting for mass percent is 1%~3%.
(3) mixing for above-mentioned vitreosol being placed in water or second alcohol and water in heating evaporation colloidal sol in water-bath or oil bath is molten
Agent obtains loose, foam-like gel, and temperature when evaporating solvent is 80~160 DEG C.
(4) this gel is placed in 250~500 DEG C of Muffle furnace, or is placed directly in micro-wave oven, low-temperature burning reaction occurs
Obtain required nanoscale, porous (CoCrFeMnNi) with rock-salt type structure3O4High entropy oxide powder material.Wherein:
The reaction time is 15~30min in Muffle furnace；Microwave input power is 500~700W, and the reaction time is 4~10min.
The fuel is one of tartaric acid, citric acid, glucose, pregnancy urotropine and ethylenediamine tetra-acetic acid or several
The mixing of kind.
The combustion adjuvant is one or both of ammonium acetate or ammonium nitrate.
The basic principle that the present invention can prepare porous material is: fuel is under the action of extraneous primary power, very short
It carries out having the oxidation-reduction reaction of self- propagating property to burn in time, and releases a large amount of gas, thus in solid product
It is middle to generate a large amount of hole.
Compared with prior art, the beneficial effects of the present invention are:
1, using low-temperature combustion synthesis (Low-temperature Combustion Synthesis, be abbreviated as LCS)
It is prepared for the above-mentioned material with porous structure.After lower temperature (250-500 DEG C) ignites, made instead using own combustion heat release
Spontaneous progress is answered, conbustion synthesis speed is fast, and dispersion degree is high so that the product of preparation has, chemical uniformity is good and partial size is carefully etc. special
Point.
2, raw material use liquid phase ingredient, it is ensured that raw material reaches molecular level mixing, and product realizes stoichiometric ratio.
3, Electrochemical results are shown, spinel-type of the present invention is porous (CoCrCuFeNi)3O4High entropy oxide material tool
There is higher initial discharge capacity (1230~1400mAhg-1) and preferable cycle performance.
Detailed description of the invention
Fig. 1 is made from embodiment 1 (CoCrCuFeNi)3O4The XRD diagram piece of high entropy oxide material.
Fig. 2 is made from embodiment 1 (CoCrCuFeNi)3O4The SEM picture of high entropy oxide material.
Fig. 3 is made from embodiment 2 (CoCrCuFeNi)3O4The SEM picture of high entropy oxide material.
Fig. 4 is made from embodiment 3 (CoCrCuFeNi)3O4The SEM picture of high entropy oxide material.
Specific embodiment
The present invention is described in detail below in conjunction with specific embodiment, but the present invention is not limited to following embodiments.
Embodiment 1
Weigh the Co (NO of 29.01g3)2·6H2O, the Cr (NO of 40.02g3)3·9H2O, the Cu (NO of 24.16g3)2·
3H2O, the Fe (NO of 40.4g3)3·9H2Ni (the NO of O and 29.08g3)2·6H2O is dissolved in 50mL distilled water and the ethyl alcohol of 50mL is molten
In liquid, it is uniformly mixing to obtain the mixed solution containing metal salt；Then it weighs 38.42g citric acid and 54.05g glucose is added
In above-mentioned mixed solution, it is after mixing evenly 8 with the pH that ammonium hydroxide adjusts mixed solution, obtains transparent colloidal sol；It then will be above-mentioned
Vitreosol, which is placed in 160 DEG C of oil bath, to be heated to remove aqueous solvent, and loose, foam-like gel is obtained；It finally will be above-mentioned solidifying
Glue is placed in 250 DEG C of Muffle furnace reaction 30min, obtains final products.XRD spectra (Fig. 1) shows prepared
(CoCrCuFeNi)3O4High entropy oxide material is spinel structure, and SEM picture (Fig. 2) shows prepared
(CoCrCuFeNi)3O4The average grain diameter of high entropy oxide material is 120nm, and pattern is spherical and has porous structure.
Embodiment 2
Weigh the Co (NO of 29.01g3)2·6H2O, the Cr (NO of 40.02g3)3·9H2O, the Cu (NO of 24.16g3)2·
3H2O, the Fe (NO of 40.4g3)3·9H2Ni (the NO of O and 29.08g3)2·6H2O is dissolved in 50mL distilled water, is uniformly mixing to obtain
Mixed solution containing metal salt；Then 180.16g glucose, 1.8g ammonium nitrate and 1.8g ammonium acetate are weighed, above-mentioned mixing is added
In solution, it is after mixing evenly 7 with the pH that ammonium hydroxide adjusts mixed solution, obtains transparent colloidal sol；Then by above-mentioned vitreosol
It is placed in 90 DEG C of water-bath and heats to remove aqueous solvent, obtain loose, foam-like gel；Above-mentioned gel is finally placed in 500
DEG C Muffle furnace react 15min, obtain final products.SEM picture (Fig. 3) shows prepared (CoCrCuFeNi)3O4High entropy oxygen
The average grain diameter of compound material is 80nm, and pattern is spherical and has porous structure.
Embodiment 3
Weigh the Co (NO of 43.66g3)2·6H2O, the Cr (NO of 60.02g3)3·9H2O, the Cu (NO of 36.24g3)2·
3H2O, the Fe (NO of 60.6g3)3·9H2Ni (the NO of O and 43.62g3)2·6H2O is dissolved in 80mL distilled water and 20mL ethanol solution
In, it is uniformly mixing to obtain the mixed solution containing metal salt；Then it weighs 168.9g tartaric acid and the addition of 3.38g ammonium nitrate is above-mentioned
In mixed solution, it is after mixing evenly 7 with the pH that ammonium hydroxide adjusts mixed solution, obtains transparent colloidal sol；It then will be above-mentioned transparent
Colloidal sol, which is placed in 120 DEG C of oil bath, to be heated to remove aqueous solvent, and loose, foam-like gel is obtained；Finally above-mentioned gel is set
8min is reacted in the micro-wave oven that input power is 600W, obtains final products.SEM picture (Fig. 4) shows prepared
(CoCrCuFeNi)3O4The average grain diameter of high entropy oxide material is 60nm, and pattern is spherical and has porous structure.
Claims (4)
1. a kind of preparation method of the porous high entropy oxide material of lithium ion battery negative material spinel-type, it is characterised in that packet
Include following steps:
(1) nitrate for weighing Co, Cr, Cu, Fe and Ni of equimolar amounts is dissolved in distilled water or ethanol water, and stirring is equal
It is even, obtain the mixed solution containing metal salt；
Wherein: volume fraction of ethanol is 20~80% in ethanol water；The concentration of the metal salt is 1~2mol/L；
(2) it is mixed that the mixture of fuel or fuel and combustion adjuvant is weighed in above-mentioned mixed solution, stir evenly and ammonium hydroxide adjusting is added
The pH to 6~8 for closing solution, obtains transparent colloidal sol；
The molar ratio of metal ion in the fuel and mixed solution is 1~2: 1；The mixture of the fuel and combustion adjuvant
In: mass percent shared by combustion adjuvant is 1~3%；
(3) above-mentioned vitreosol is placed in water-bath or oil bath the mixed solvent of water or second alcohol and water in heating evaporation colloidal sol, obtained
Obtain loose, foam-like gel；
(4) gel that step (3) obtains is placed in 250~500 DEG C of Muffle furnace or be placed directly in micro-wave oven, low temperature combustion occurs
Product is obtained after burning reaction；
Wherein: the reaction time is 15~30min in Muffle furnace；Microwave input power be 500~700W, the reaction time be 4~
10min。
2. the preparation side of the porous high entropy oxide material of lithium ion battery negative material spinel-type according to claim 1
Method, it is characterised in that: the fuel is one in tartaric acid, citric acid, glucose, pregnancy urotropine and ethylenediamine tetra-acetic acid
Kind is several.
3. the preparation side of the porous high entropy oxide material of lithium ion battery negative material spinel-type according to claim 1
Method, it is characterised in that: the combustion adjuvant is one or both of ammonium acetate and ammonium nitrate.
4. the preparation side of the porous high entropy oxide material of lithium ion battery negative material spinel-type according to claim 1
Method, it is characterised in that: the temperature of step (3) the evaporation solvent is 80~160 DEG C.
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