CN108933248A - A kind of preparation method of the spherical high entropy oxide material of lithium ion battery negative material spinel-type - Google Patents
A kind of preparation method of the spherical high entropy oxide material of lithium ion battery negative material spinel-type Download PDFInfo
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- CN108933248A CN108933248A CN201810815366.2A CN201810815366A CN108933248A CN 108933248 A CN108933248 A CN 108933248A CN 201810815366 A CN201810815366 A CN 201810815366A CN 108933248 A CN108933248 A CN 108933248A
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- lithium ion
- ion battery
- high entropy
- battery negative
- entropy oxide
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- 239000000463 material Substances 0.000 title claims abstract description 41
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011651 chromium Substances 0.000 claims abstract description 8
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 5
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 3
- 150000003891 oxalate salts Chemical class 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- FBHNJVAPQXOPOB-UHFFFAOYSA-L [Na+].[Na+].OS(=O)S(O)=O.[O-]S(=O)S([O-])=O Chemical compound [Na+].[Na+].OS(=O)S(O)=O.[O-]S(=O)S([O-])=O FBHNJVAPQXOPOB-UHFFFAOYSA-L 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000006479 redox reaction Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 229910052596 spinel Inorganic materials 0.000 description 6
- 239000011029 spinel Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- -1 thio sulphur Chemical compound 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 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
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910016287 MxOy Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Iron (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of preparation methods of the spherical high entropy oxide material of lithium ion battery negative material spinel-type, belong to lithium ion battery negative material field.The method is combined using chemical reduction method and Low Temperature Heat Treatment, specifically: using the chlorate of cobalt, chromium, copper, iron and nickel, sulfate, nitrate, carbonate, acetate and oxalates as source metal, then the product that redox reaction occurs is calcined in 300~500 DEG C of equipment as reducing agent and obtains target product by sodium borohydride and sodium hydrosulfite sodium dithionite.The preparation method uses liquid phase ingredient, it is ensured that raw material reaches molecular level mixing, and product realizes stoichiometric ratio；Have the characteristics that simultaneously simple process, reaction is mild, the time is short, it is high-efficient and to calciner without particular/special requirement.High entropy oxide powder purity is high prepared by the present invention, granularity be small and initial discharge capacity with higher and preferable cycle performance.
Description
Technical field
The invention belongs to lithium ion battery negative material fields, and in particular to one kind has spinel type crystal structure and ball
(CoCrCuFeNi) of shape pattern3O4High entropy oxide material and preparation method thereof.
Background technique
Lithium ion battery is newest generation battery, light-weight, small in size, energy after nickel chromium triangle, nickel-metal hydride battery
The characteristic that density is high, cycle performance is good and self-discharge rate is small, by portable electronic products such as mobile phone, laptops
And the extensive pro-gaze in the fields such as new-energy automobile.Lithium ion battery success application a key be exactly cathode insertion and
Deintercalation lithium compound.Therefore negative electrode material is as one of big composition material of lithium battery four, in the capacity and circulation for improving battery
Aspect of performance plays important function, and performance directly affects the performance of lithium ion battery.
Commercial lithium ion battery negative material is generally graphite-like carbon negative pole material at present.But graphite-based negative electrode material
Theoretical specific capacity is low, only 372mAhg-1；Although on the other hand its biggish layer structure provides place for the storage of lithium,
It is unfavorable for battery and relevant apparatus to develop to miniaturization；Electricity of the intercalation potential of graphite-based cathode close to lithium metal simultaneously
Position, is unfavorable for the safety of battery.It is above-mentioned that there are problems strictly to limit the development of the following lithium ion battery.Therefore exploitation has more
The lithium ion battery negative material of high capacity, it is extremely urgent if transition metal oxide negative electrode material.
French scientist Tarascon in 2000 etc. uses CoO, Co2O3、Fe2O3, the single transition oxide such as CuO and MnO
As ion cathode material lithium, such electrode material is due to the electron rich transfer process of correspondence, thus theory with higher is held
Amount, if the theoretical capacity of CuO is 674mAhg-1.Chinese Patent Application No. discloses a kind of transition metal for 201410276284.7
Oxide MxOyThe lithium ion battery negative material of (M Fe, one or more of Mn and Cr).It develops again on this basis
Binary lithium ion battery negative material, as Liu Lei is prepared for NiFe with hydrothermal synthesis method2O4、ZnFe2O4、CoxFe3-xO4、
CoxMn3-xO4And wait the negative electrode material (Liu of the binary oxide with spinel structure of binary series as lithium ion battery
Structure design and the university of the Electrochemical Properties Chinese Academy of Sciences of lithium ion battery transition metal oxide negative electrode material of heap of stone
Ph.D. Dissertation, 2015.).High entropy oxide material is a kind of new ceramics to grow up on the basis of high-entropy alloy
Material is proposed the concept of this new ceramic material of high entropy oxide by the Christina M.Rost in the U.S. first.It closes at present
Also seldom as the report of lithium ion battery negative material in high entropy oxide, only Chinese Patent Application No. is
201711421445.7 proposing to be prepared for using the laser molecular beam epitaxy precipitation method for lithium ion battery negative material
(MgCoNiCuZn) O high entropy oxide film material.It still yet there are no lithium ion battery negative material spinel-type at present
(CoCrCuFeNi)3O4The relevant report of high entropy oxide material and preparation method.
Summary of the invention
The technical problem to be solved by the present invention is to design novel lithium ion battery negative material, one kind having spinelle
(CoCrCuFeNi) of type crystal structure and spherical morphology3O4High entropy oxide material；Lacking for prior art preparation is overcome simultaneously
Point provides a kind of high entropy oxide powder material that low energy consumption, high production efficiency, environmentally protective, product are post-processed without complexity
Preparation method.
It is spherical (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) metal salt for weighing the cobalt of certain mass equimolar ratio, chromium, copper, iron and nickel is dissolved in the mixed of water or water and ethyl alcohol
It closes in solution, is heated to make it completely dissolved, used after mixing as oxidation solution；The concentration of the metal salt is 0.1
~0.3mol/L.
(3) it weighs after a certain amount of NaOH is dissolved in water, reducing agent is added, and surfactant is added, makees after mixing
For reducing solution use；The dosage of surfactant is 2~the 5 ‰ of reducing solution quality；The molar ratio of the reducing agent and NaOH
It is 1: 2~3；The concentration of the reducing agent is 0.1~0.5mol/L；The molar ratio of the reducing agent and step (1) metal salt is 1
: 1~1.5.
(3) oxidation solution in step (1) is added drop-wise to reducing solution prepared by step (2) with the speed of 10~30mL/min
In, and the magnetic agitation under 20~60 DEG C of reaction temperature, continue 20~40min of stirring after dripping and be aged 30~60min,
Product is obtained in 300~500 DEG C of calcinings after centrifuge separation.
The cobalt, chromium, copper, iron and nickel metal salt be corresponding chlorate, sulfate, nitrate, carbonate, acetate
Or oxalates.
The surfactant is polyvinylpyrrolidone, glycerol, polyethylene glycol or sorbierite.
The reducing agent is sodium borohydride or sodium thiosulfate.
Compared with prior art, the present invention has following technical effect that
1, the present invention develops spinel-type (CoCrCuFeNi)3O4High entropy oxide ion cathode material lithium, and use liquid
Phase reduction method+low-temperature sintering method is prepared for having the high entropy oxide material of the transition metal of spinel structure；It is simple process, anti-
Should it is mild, the time is short, it is high-efficient and to calciner without particular/special requirement.
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, are somebody's turn to do (CoCrCuFeNi)3O4High entropy oxide material initial discharge with higher
Capacity (1340~1520mAhg-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.
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 CoCl of the 11.90g of equimolar amounts2·6H2O, the CrCl of 13.32g3·6H2O, the CuCl of 7.95g2·
2H2O, the FeCl of 13.52g3·6H2The NiCl of O and 11.89g2·6H2Five kinds of metal salts of O, are dissolved in 250mL distilled water,
It is used after mixing as oxidation solution；The NaOH for weighing 20.4g is dissolved in 1700mLH2After in O, the thio sulphur of 26.35g is added
Sour sodium and 0.14g surfactant polyvinylpyrrolidone are used as reducing solution after mixing；By above-mentioned oxidation solution with
The speed of 15mL/min is added drop-wise in reducing solution, and the magnetic agitation under 60 DEG C of reaction temperature, continues to stir after dripping
30min is simultaneously aged 30min, calcines in 300 DEG C of Muffle furnaces after centrifuge separation, 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 60nm, and pattern is spherical shape.
Embodiment 2
Weigh the Co (NO of the 43.66g of equimolar amounts3)2·6H2O, the Cr (NO of 60.18g3)3·9H2O, the Cu of 36.24g
(NO3)2·3H2O, the Fe (NO of 60.6g3)3·9H2Ni (the NO of O and 43.62g3)2·6H2Five kinds of metal salts of O, are dissolved in
In 250mL distilled water, used after mixing as oxidation solution；The NaOH for weighing 75g is dissolved in 2500mLH2After in O, it is added
The sodium borohydride and 1.78g surfactant polyethylene of 28.37g is used as reducing solution after mixing；By above-mentioned oxidation
Liquid is added drop-wise in reducing solution with the speed of 30mL/min, and the magnetic agitation under 20 DEG C of reaction temperature, continues to stir after dripping
It mixes 40min and is aged 60min, calcined in 500 DEG C of Muffle furnaces after centrifuge separation, obtained with spinel structure, average grain
Diameter is the spherical shape (CoCrCuFeNi) of 110nm3O4High entropy oxide material.
Embodiment 3
Weigh the CoSO of the 11.24g of equimolar amounts4·7H2O, Cr (OH) SO of 6.60g4, 9.99g CuSO4·5H2O、
11.12g FeSO4·7H2The NiSO of O and 10.51g4·6H2Five kinds of metal salts of O, are dissolved in 200mL distilled water, mixing
It is used after uniformly as oxidation solution；The NaOH for weighing 16g is dissolved in 320mLH2After in O, the sodium borohydride and 1.03g of 6.05g is added
Surfactant sorbierite is used as reducing solution after mixing；Above-mentioned oxidation solution is added drop-wise to the speed of 10mL/min
In reducing solution, and the magnetic agitation under 40 DEG C of reaction temperature, continue to stir 60min after dripping and is aged 40min, centrifugation point
It is calcined in 400 DEG C of Muffle furnaces from after, obtains the spherical shape that there is spinel structure, average grain diameter is 75nm
(CoCrCuFeNi)3O4High entropy oxide material.
Claims (4)
1. a kind of preparation method of the spherical high entropy oxide material of lithium ion battery negative material spinel-type, it is characterised in that packet
Include following steps:
(1) metal salt for weighing the cobalt of certain mass equimolar ratio, chromium, copper, iron and nickel is dissolved in water or water and the mixing of ethyl alcohol is molten
It in liquid, is heated to make it completely dissolved, be used after mixing as oxidation solution；
The concentration of the metal salt is 0.1~0.3mol/L；
(2) it weighs after a certain amount of NaOH is dissolved in water, reducing agent is added, and surfactant is added, after mixing as also
Stoste uses；
The dosage of surfactant is 2~the 5 ‰ of reducing solution quality；The molar ratio of the reducing agent and NaOH are 1: 2~3；
The concentration of the reducing agent is 0.1~0.5mol/L；The molar ratio of the reducing agent and step (1) metal salt is 1: 1~1.5；
(3) oxidation solution in step (1) is added drop-wise in reducing solution prepared by step (2) with the speed of 10~30mL/min,
And the magnetic agitation under 20~60 DEG C of reaction temperature, continue 20~40min of stirring after dripping and is aged 30~60min, from
Product is obtained in 300~500 DEG C of calcinings after heart separation.
2. the preparation side of the spherical high entropy oxide material of lithium ion battery negative material spinel-type according to claim 1
Method, which is characterized in that the cobalt, chromium, copper, iron and nickel metal salt be corresponding chlorate, sulfate, nitrate, carbonate,
Acetate or oxalates.
3. the preparation side of the spherical high entropy oxide material of lithium ion battery negative material spinel-type according to claim 1
Method, which is characterized in that the surfactant is polyvinylpyrrolidone, glycerol, polyethylene glycol or sorbierite.
4. the preparation side of the spherical high entropy oxide material of lithium ion battery negative material spinel-type according to claim 1
Method, which is characterized in that the reducing agent is sodium borohydride or sodium thiosulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810815366.2A CN108933248B (en) | 2018-07-23 | 2018-07-23 | Preparation method of spinel-type spherical high-entropy oxide material as negative electrode material of lithium ion battery |
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| CN110556536A (en) * | 2019-09-19 | 2019-12-10 | 安徽工业大学 | Six-element high-entropy oxide material for lithium ion battery and preparation method thereof |
| CN110600724A (en) * | 2019-09-19 | 2019-12-20 | 安徽工业大学 | Five-element transition-non-transition high-entropy oxide negative electrode material for lithium ion battery |
| CN111333124A (en) * | 2020-03-06 | 2020-06-26 | 西安交通大学 | Spinel-type mesoporous high-entropy oxide nanosphere with hollow structure and preparation method and application thereof |
| CN111348910A (en) * | 2020-03-10 | 2020-06-30 | 南昌航空大学 | Hexahydric spinel type iron-cobalt-chromium-manganese-nickel-copper series high-entropy oxide and powder preparation method thereof |
| CN111620681A (en) * | 2020-06-16 | 2020-09-04 | 湖南大学 | Preparation method of high-entropy oxide material |
| CN113461415A (en) * | 2021-07-19 | 2021-10-01 | 中国科学院兰州化学物理研究所 | Hydrothermal method for preparing high-entropy oxide material (MAlFeCuMg)3O4Method (2) |
| CN113621988A (en) * | 2021-08-11 | 2021-11-09 | 东北大学秦皇岛分校 | High-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst and preparation method and application thereof |
| CN114618522A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Method for preparing metal oxide loaded high-entropy alloy and synthesizing methyl propionate |
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| CN109748303B (en) * | 2019-03-19 | 2022-02-08 | 大连交通大学 | Preparation method of high-purity spherical magnesia-alumina spinel nano-powder |
| CN109748303A (en) * | 2019-03-19 | 2019-05-14 | 大连交通大学 | The preparation method of high pure spherical magnesia alumina spinel nanopowder |
| CN110556536B (en) * | 2019-09-19 | 2022-06-14 | 安徽工业大学 | Six-element high-entropy oxide material for lithium ion battery and preparation method thereof |
| CN110556536A (en) * | 2019-09-19 | 2019-12-10 | 安徽工业大学 | Six-element high-entropy oxide material for lithium ion battery and preparation method thereof |
| CN110600724A (en) * | 2019-09-19 | 2019-12-20 | 安徽工业大学 | Five-element transition-non-transition high-entropy oxide negative electrode material for lithium ion battery |
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| CN111348910A (en) * | 2020-03-10 | 2020-06-30 | 南昌航空大学 | Hexahydric spinel type iron-cobalt-chromium-manganese-nickel-copper series high-entropy oxide and powder preparation method thereof |
| CN111348910B (en) * | 2020-03-10 | 2022-08-12 | 南昌航空大学 | Hexahydric spinel type iron-cobalt-chromium-manganese-nickel-copper series high-entropy oxide and powder preparation method thereof |
| CN111620681A (en) * | 2020-06-16 | 2020-09-04 | 湖南大学 | Preparation method of high-entropy oxide material |
| CN114618522A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Method for preparing metal oxide loaded high-entropy alloy and synthesizing methyl propionate |
| CN114618522B (en) * | 2020-12-11 | 2023-06-20 | 中国科学院大连化学物理研究所 | Method for preparing and synthesizing methyl propionate by using metal oxide loaded high-entropy alloy |
| CN113461415A (en) * | 2021-07-19 | 2021-10-01 | 中国科学院兰州化学物理研究所 | Hydrothermal method for preparing high-entropy oxide material (MAlFeCuMg)3O4Method (2) |
| CN113621988B (en) * | 2021-08-11 | 2022-07-08 | 东北大学秦皇岛分校 | High-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst and preparation method and application thereof |
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