CN115050947A - Modified ferrate cathode material, preparation method thereof and lithium ion battery - Google Patents
Modified ferrate cathode material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN115050947A CN115050947A CN202210909615.0A CN202210909615A CN115050947A CN 115050947 A CN115050947 A CN 115050947A CN 202210909615 A CN202210909615 A CN 202210909615A CN 115050947 A CN115050947 A CN 115050947A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 14
- 239000010406 cathode material Substances 0.000 title claims description 39
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 19
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 239000011258 core-shell material Substances 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 25
- 239000007774 positive electrode material Substances 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 7
- 150000004692 metal hydroxides Chemical class 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- WVEXUUSBAAAPBN-UHFFFAOYSA-N [O-2].C(C)(C)[Al+2] Chemical compound [O-2].C(C)(C)[Al+2] WVEXUUSBAAAPBN-UHFFFAOYSA-N 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 16
- 239000010405 anode material Substances 0.000 abstract description 13
- 238000000354 decomposition reaction Methods 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000010410 layer Substances 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012546 transfer Methods 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
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a modified ferrate anode material, a preparation method thereof and a lithium ion battery, wherein the modified ferrate anode material is of a core-shell structure and comprises inner core ferrate and shell layer metal oxide coated on the surface of the inner core; the coating method is liquid phase coating. The invention adopts the surface coating of the metal oxide to relieve the contact of the inner core ferrate with air and water vapor, improve the cycle performance and the storage performance of the ferrate as the anode material and reduce the self-decomposition rate.
Description
Technical Field
The invention belongs to the technical field of manufacturing of lithium ion battery anodes, relates to a modified ferrate anode material, and particularly relates to a modified ferrate anode material, a preparation method thereof and a lithium ion battery.
Background
With the widespread development of consumer electronics and new energy automobiles, the energy density of lithium ion batteries is more demanding. The lithium ion battery with high energy density needs a positive electrode material with high specific capacity to match with the lithium ion battery, LCO, LFP or NCM is taken as the positive electrode material widely applied at present, the actual specific capacity is below 200mAh/g, and the requirement of energy density is difficult to meet. Ferrate (XFeO) 4 ) The iron-based lithium iron phosphate is a novel positive electrode material, wherein Fe is in positive hexavalent state, the oxidation-reduction potential is high, and the reaction is reversible. The ferrate changes between +6 valence and +3 valence in the charging and discharging process, is a conversion type anode, and has higher theoretical specific capacity, such as K 2 FeO 4 The theoretical specific capacity of the material reaches 406mAh/g, far exceeding the currently common positive electrode materials, and K 2 FeO 4 Is a common water purifying agent, has mature and simple preparation process, low price and environmental protection, and has the potential of becoming a new generation of anode material.
Although K 2 FeO 4 Has higher oxidation-reduction potential and high specific capacity, but because Fe in the Fe alloy is in +6 valence, the Fe alloy is easy to generate self-decomposition reaction (4K) in the circulation process 2 FeO 4 ＝2Fe 2 O 3 +3O 2 +4K 2 O); on the other hand, potassium ferrate reacts very readily with water in the air (4K) 2 FeO 4 +10H 2 O═4Fe(OH) 3 ↓+8KOH+3O 2 ×) which causes K to go 2 FeO 4 The storage is difficult, the cycling stability is poor (only 100 cycles can be cycled), at present, researchers have few researches on the ferrate positive electrode material, and common modification technologies such as surface coating and doping for the ferrate positive electrode material are not applied to the ferrate.
CN 105047876A discloses a preparation method of a composite cathode material of a ferrate battery, wherein a layer of conductive polymer is coated on the surface of potassium ferrate, the conductive polymer can prevent the potassium ferrate from contacting with electrolyte, simultaneously the conductivity of the electrode material is enhanced, the charge transfer resistance in the electrode is reduced, the utilization rate of the ferrate cathode material is improved, and the ferrate cathode material is used as the cathode material of an alkaline ferrate battery, so that the development and the application of the ferrate battery have wide prospects.
CN 112447954A relates to a graphene modified ferrate material and a preparation method and application thereof, and the method comprises the following steps: preparing strong acid graphite oxide, washing the strong acid graphite oxide for multiple times by using a mixed solution containing nitrogen methyl pyrrolidone and absolute ethyl alcohol to obtain neutral graphite oxide, and uniformly dispersing the neutral graphite oxide by using water to obtain a graphite oxide water dispersion solution; reducing graphite oxide in the graphite oxide aqueous dispersion into chemically reduced graphene under an ultrasonic-assisted hydrothermal condition by using ascorbic acid as a reducing agent, and then performing suction filtration and drying to obtain the chemically reduced graphene; and (3) preparing the ferrate material modified by the graphene from ferrate and chemically reduced graphene ethanol dispersion liquid by a codeposition method. According to the invention, the chemical reduction graphene is coated on the surface of ferrate by a codeposition method, so that the stability of ferrate in a humid environment and a saturated KOH solution is obviously improved, and the actual discharge performance of an alkaline super-iron battery consisting of the ferrate and Zn under various conditions is improved.
In the technical scheme, the storage performance and the cycle performance of the ferrate as a positive electrode material are not improved, and intrinsic defects of the ferrate, such as easy decomposition in water, easy self-discharge decomposition and the like, are not fully considered.
Therefore, how to improve the storage performance and the cycle performance of the ferrate as the cathode material and fully avoid the intrinsic defect of the ferrate in the preparation process is a problem to be solved in the technical field of the manufacture of the cathode material of the lithium ion battery.
Disclosure of Invention
In order to solve the technical problems, the invention provides a modified ferrate cathode material, a preparation method thereof and a lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a modified ferrate cathode material, which is of a core-shell structure and comprises inner core ferrate and a shell layer metal oxide coated on the surface of the inner core;
the coating method is liquid phase coating.
The invention adopts the surface coating of the metal oxide to relieve the contact of the inner core ferrate with air and water vapor, improve the cycle performance and the storage performance of the ferrate as the anode material and reduce the self-decomposition rate.
Compared with the traditional solid phase coating, the liquid phase coating method is easier to form a core-shell structure, and the coating layer has the characteristics of more uniformity, stability and compactness.
Preferably, the metal in the metal oxide comprises aluminum.
Preferably, the mass of the metal oxide in the modified ferrate positive electrode material is 2 to 5 wt% in mass percentage, for example, 2 wt%, 2.5 wt%, 3 wt%, 4 wt% or 5 wt%, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the weight of ferrate in the modified ferrate positive material is 95-98 wt%, for example 95 wt%, 95.5 wt%, 96 wt%, 97 wt% or 98 wt%, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the particle size of the modified ferrate cathode material is 5-10 μm, such as 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm, but not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the shell thickness of the modified ferrate cathode material is 15-60 nm, such as 15nm, 20nm, 25nm, 30nm, 40nm, 50nm, 55nm or 60nm, but not limited to the values listed, and other values not listed in the range of values are also applicable.
In a second aspect, the present invention provides a method for preparing the modified ferrate cathode material according to the first aspect, wherein the method comprises the following steps:
(1) mixing a metal source, a ferrate feedstock, and a solvent to obtain a mixture;
(2) calcining the mixture obtained in the step (1) to obtain the modified ferrate cathode material.
In the invention, ferrate and a metal source are premixed in a solvent, and then a solid mixture premixed in the solvent is obtained, so that the ferrate is prevented from self-decomposition at high temperature or in the preparation process, and the yield is improved.
Preferably, the metal source in step (1) comprises any one of or a combination of at least two of metal oxide, metal hydroxide, metal isopropyl oxide or metal salt, and typical but non-limiting combinations include a combination of metal oxide and metal hydroxide, a combination of metal hydroxide and metal isopropyl oxide, a combination of metal isopropyl oxide and metal salt, a combination of metal oxide, metal hydroxide and metal isopropyl oxide, a combination of metal hydroxide, metal isopropyl oxide and metal salt, or a combination of metal oxide, metal hydroxide, metal isopropyl oxide and metal salt.
Preferably, the metal in the metal source of step (1) comprises an aluminum source.
Preferably, the solvent of step (1) comprises an organic solvent.
Preferably, the organic solvent in step (1) comprises any one of methanol, ethanol or acetone or a combination of at least two thereof, and typical but non-limiting combinations include a combination of methanol and ethanol, a combination of ethanol and acetone, a combination of methanol and acetone, or a combination of methanol, ethanol and acetone.
Preferably, the particle size of the ferrate starting material in step (1) is in the range of 5 to 10 μm, such as 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm, but not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the liquid-solid ratio of the metal source to the solvent in step (1) is 35-85 mL/g, such as 35mL/g, 45mL/g, 55mL/g, 65mL/g, 75mL/g or 85mL/g, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the liquid-solid ratio of the ferrate raw material to the solvent in step (1) is 2-5 mL/g, such as 2mL/g, 2.5mL/g, 3mL/g, 4mL/g or 5mL/g, but not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the mixing of step (1) is performed under an inert gas and/or nitrogen atmosphere.
Preferably, the inert gas comprises argon and/or helium.
Preferably, the mixing in step (1) further comprises stirring.
Preferably, the rotation speed of the stirring is 200-500 r/min, such as 200r/min, 250r/min, 300r/min, 400r/min or 500r/min, but not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the stirring time is 3-5 h, for example, 3h, 3.5h, 4h, 4.5h or 5h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the calcination of step (2) is carried out under an ozone atmosphere.
In the invention, the ferrate is prevented from self-decomposition in the high-temperature calcination process by calcining in ozone, thereby improving the yield.
Preferably, the calcination of step (2) includes a temperature-raising process and a constant-temperature process.
Preferably, the temperature raising rate of the temperature raising process is 3 to 10 ℃/min, for example, 3 ℃/min, 5 ℃/min, 7 ℃/min, 8 ℃/min or 10 ℃/min, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the temperature of the end point of the temperature raising process is 700 to 900 ℃, for example, 700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the thermostatic process is carried out under a mixed atmosphere of ozone and a protective gas.
In the constant-temperature calcination process, the structural stability of the ferrate is ensured by the mixed atmosphere of ozone and protective gas, so that the modified ferrate cathode material with a stable structure and a controllable particle size range is obtained after sintering.
Preferably, the protective gas comprises argon and/or nitrogen.
Preferably, the time of the constant temperature process is 3-5 h, for example, 3h, 3.5h, 4h, 4.5h or 5h, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the calcining in the step (2) further comprises washing and drying.
Preferably, the washing liquid for washing comprises an organic solvent.
Preferably, the temperature of the drying is 40 to 60 ℃, for example, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the drying time is 2-4 h, for example, 2h, 2.5h, 3h, 3.5h or 4h, but not limited to the recited values, and other values in the range of the values are also applicable.
As a preferable technical solution of the preparation method of the second aspect of the present invention, the preparation method comprises the steps of:
(1) mixing an aluminum source, a ferrate raw material and an organic solvent in an inert gas atmosphere, and stirring at a rotating speed of 200-500 rpm for 3-5 hours to obtain a mixture;
(2) heating the mixture obtained in the step (1) to 700-900 ℃ at a speed of 3-10 ℃/min in an ozone atmosphere, introducing argon and/or nitrogen, calcining at a constant temperature for 3-5 h, cleaning with an organic solvent, and drying at 40-60 ℃ for 2-4 h to obtain the modified ferrate positive electrode material;
the particle size range of the ferrate raw material in the step (1) is 5-10 mu m; the aluminum source comprises any one of aluminum oxide, aluminum hydroxide, isopropyl aluminum oxide or aluminum salt or a combination of at least two of the aluminum oxide, the aluminum hydroxide, the isopropyl aluminum oxide or the aluminum salt; the organic solvent comprises any one of methanol, ethanol or acetone; the liquid-solid ratio of the aluminum source to the organic solvent is 35-85 mL/g; the liquid-solid ratio of the ferrate raw material to the organic solvent is 2-5 mL/g.
In a third aspect, the present invention provides a lithium ion battery, wherein the lithium ion battery contains the modified ferrate positive electrode material according to the first aspect.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the invention adopts the surface coating of the metal oxide to relieve the contact of the inner core ferrate with air and water vapor, improve the cycle performance and the storage performance of the ferrate as the anode material and reduce the self-decomposition rate.
(2) The invention adopts liquid phase coating and calcinations under ozone atmosphere, which ensures the structural stability of ferrate, and obtains the modified ferrate anode material with stable structure and controllable particle size range after sintering.
(3) The specific capacity of the modified ferrate positive electrode material provided by the invention can reach 210mAh/g after the cycle of 250 weeks.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Example 1
The embodiment provides a modified ferrate cathode material, which is of a core-shell structure and comprises a core of potassium ferrate and a shell layer of aluminum oxide coated on the surface of the core.
Calculated by mass ratio fraction, the mass of the aluminum oxide is 3.5 wt%, and the mass of the potassium ferrate is 96.5 wt%.
The shell thickness of the modified ferrate cathode material is 30 nm.
The preparation method comprises the following steps:
(1) mixing aluminum hydroxide, potassium ferrate and methanol under the atmosphere of argon gas, and stirring at the rotating speed of 350 revolutions per minute for 4 hours to obtain a mixture;
(2) heating the mixture obtained in the step (1) to 800 ℃ at the speed of 6.5 ℃/min under the ozone atmosphere, introducing argon, calcining at constant temperature for 4h, cleaning with methanol and drying to obtain the modified ferrate anode material;
the particle size range of the potassium ferrate in the step (1) is 5-10 mu m; the liquid-solid ratio of the aluminum hydroxide to the methanol is 60 mL/g; the liquid-solid ratio of the potassium ferrate to the methanol is 3.5 mL/g.
Example 2
The embodiment provides a modified ferrate cathode material, which is of a core-shell structure and comprises a core of potassium ferrate and a shell layer of aluminum oxide coated on the surface of the core.
The mass of the aluminum oxide is 2 wt%, and the mass of the potassium ferrate is 98 wt%.
The shell layer thickness of the modified ferrate anode material is 15 nm.
The preparation method comprises the following steps:
(1) mixing aluminum oxide, potassium ferrate and ethanol in a helium atmosphere, and stirring at the rotating speed of 200 revolutions per minute for 5 hours to obtain a mixture;
(2) heating the mixture obtained in the step (1) to 700 ℃ at a speed of 3 ℃/min under an ozone atmosphere, introducing nitrogen, calcining at a constant temperature for 5h, cleaning with ethanol, and drying to obtain the modified ferrate cathode material;
the particle size range of the ferrate raw material in the step (1) is 5-10 mu m; the liquid-solid ratio of the aluminum trioxide to the ethanol is 85 mL/g; the liquid-solid ratio of the potassium ferrate to the ethanol is 2 mL/g.
Example 3
The embodiment provides a modified ferrate cathode material, which is of a core-shell structure and comprises a core of potassium ferrate and a shell layer of aluminum oxide coated on the surface of the core.
The mass of the aluminum oxide is 5 wt%, and the mass of the potassium ferrate is 95 wt%.
The shell layer thickness of the modified ferrate anode material is 60 nm.
The preparation method comprises the following steps:
(1) mixing aluminum isopropoxide, potassium ferrate and acetone in a nitrogen atmosphere, and stirring at the rotating speed of 500 revolutions per minute for 3 hours to obtain a mixture;
(2) heating the mixture obtained in the step (1) to 900 ℃ at a speed of 10 ℃/min under an ozone atmosphere, introducing nitrogen, calcining for 3h at a constant temperature, cleaning with acetone, and drying to obtain the modified ferrate cathode material;
the particle size range of the ferrate raw material in the step (1) is 5-10 mu m; the liquid-solid ratio of aluminum isopropoxide to acetone is 35 mL/g; the liquid-solid ratio of the potassium ferrate to the acetone is 5 mL/g.
Example 4
This example provides a modified ferrate cathode material, differing from example 1 only in that the solvent was replaced with N, N-dimethylformamide in step (1) of the preparation method.
Example 5
This example provides a modified ferrate cathode material, differing from example 1 only in that ozone was replaced with nitrogen in step (2) of the preparation method.
Example 6
The embodiment provides a modified ferrate cathode material, which is different from the embodiment 1 only in that the particle size of potassium ferrate in the step (1) in the preparation method is in a range of 2-4 μm.
Example 7
The embodiment provides a modified ferrate cathode material, which is different from the embodiment 1 only in that the particle size of potassium ferrate in the step (1) in the preparation method is 12-20 μm.
Example 8
This example provides a modified ferrate positive electrode material, which is different from example 1 only in that the temperature increase rate in step (2) of the preparation method is 2 ℃/min.
Example 9
This example provides a modified ferrate positive electrode material, which is different from example 1 only in that the temperature increase rate in step (2) of the preparation method is 12 ℃/min.
Example 10
The embodiment provides a modified ferrate cathode material, which is different from the modified ferrate cathode material in embodiment 1 in that the thickness of alumina of a shell layer is 10nm, and the mass of the alumina is 1.5 wt%.
Example 11
The embodiment provides a modified ferrate cathode material, which is different from the modified ferrate cathode material in embodiment 1 in that the thickness of alumina of a shell layer is 70nm, and the mass of the alumina is 6.5 wt%.
Example 12
This example provides a modified ferrate cathode material, which is different from example 1 in that the alumina of the shell layer is replaced by magnesium oxide.
The preparation method differs from example 1 in that aluminum hydroxide is replaced with magnesium hydroxide of equal mass in step (1).
Comparative example 1
This comparative example provides a modified ferrate cathode material, differing from example 1 only in that no methanol was mixed in step (1).
And (3) preparing a positive plate from the modified ferrate positive material to assemble a half-cell, and carrying out electrochemical performance test.
And (3) testing conditions are as follows: testing the specific capacity of the alloy under the condition of 0.1C after the alloy is cycled for 250 weeks; meanwhile, the modified potassium ferrate materials provided in examples and comparative examples were stored in air at 18 to 30 ℃ with a humidity of 20 to 50% and the storage time in air was measured.
TABLE 1
The following conclusions are drawn from table 1:
(1) from examples 1 to 3, it can be seen that the metal oxide surface coating adopted in the invention relieves the contact between the inner core ferrate and air and water vapor, improves the cycle performance and storage performance of the ferrate as a positive electrode material, and reduces the rate of self-decomposition.
(2) As can be seen from comparison of example 4 with example 1, when the solvent for liquid phase coating is not the preferred solvent provided by the present invention, the dispersion effect becomes poor with the same solid-to-liquid ratio, thereby affecting the coating performance, and the cycle performance and storage performance of the thus-prepared positive electrode material are poor.
(3) From the comparison between example 5 and example 1, it can be seen that since ferrate is easily decomposed at high temperature, ozone can ensure that it is not decomposed at high temperature, and nitrogen and inert gas protect it from oxidation, when the atmosphere for calcination is not ozone, ferrate is easily decomposed at high temperature, and thus the prepared cathode material has poor cycle performance and storage performance.
(4) As is apparent from comparison of examples 6 and 7 with example 1, when the particle size range of the ferrate raw material is not within the preferred range, the cycle performance and storage performance of the prepared cathode material are poor because when the particle size is too large, the surface area of the ferrate is too large, the coating agent has coating defects, and when the particle size is too small, the ferrate is easily agglomerated, and thus the coating effect can be affected.
(5) As is apparent from comparison of examples 8 and 9 with example 1, when the temperature increase rate in step (2) is not within the preferred range, the prepared positive electrode material is poor in cycle performance and storage performance, and production efficiency is affected.
(6) As is clear from comparison of examples 10 and 11 with example 1, when the thickness of the shell layer metal oxide is not within the preferable range, the thickness is too small, which affects the storage property of the positive electrode material; the excessive thickness affects the low capacity of the material.
(7) From comparison between example 12 and example 1, it is understood that when the shell metal oxide is not a preferred metal, the prepared positive electrode material is inferior in cycle performance and storage performance.
(8) As is apparent from comparison of comparative example 1 with example 1, when dry coating is employed, the cycle performance and storage performance of the positive electrode material are poor due to non-ideal coating effect and self-decomposition of ferrate at high temperature.
The invention adopts the surface coating of the metal oxide to relieve the contact of the inner core ferrate with air and water vapor, improve the cycle performance and the storage performance of the ferrate as the anode material and reduce the self-decomposition rate.
The present invention is illustrated by the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, i.e. it is not meant to imply that the present invention must rely on the above-mentioned detailed process equipment and process flow to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The modified ferrate cathode material is characterized by being of a core-shell structure and comprising inner core ferrate and shell layer metal oxide coated on the surface of the inner core;
the coating method is liquid phase coating.
2. The modified ferrate cathode material of claim 1, wherein the metal of the metal oxide comprises aluminum;
preferably, the mass of the metal oxide in the modified ferrate positive electrode material is 2-5 wt% in terms of mass percentage;
preferably, the weight of the ferrate in the modified ferrate positive material is 95-98 wt%;
preferably, the particle size of the modified ferrate positive electrode material is 5-10 μm;
preferably, the shell layer thickness of the modified ferrate positive electrode material is 15-60 nm.
3. A method for preparing the modified ferrate cathode material according to claim 1 or 2, comprising the steps of:
(1) mixing a metal source, a ferrate feedstock, and a solvent to obtain a mixture;
(2) calcining the mixture obtained in the step (1) to obtain the modified ferrate cathode material.
4. The method according to claim 3, wherein the metal source of step (1) comprises any one or a combination of at least two of a metal oxide, a metal hydroxide, a metal isopropyl oxide, or a metal salt;
preferably, the metal in the metal source of step (1) comprises an aluminum source;
preferably, the solvent of step (1) comprises an organic solvent;
preferably, the organic solvent in step (1) comprises any one of methanol, ethanol or acetone or a combination of at least two of them.
5. The method according to claim 3 or 4, wherein the ferrate starting material of step (1) has a particle size ranging from 5 to 10 μm;
preferably, the liquid-solid ratio of the metal source to the solvent in the step (1) is 35-85 mL/g;
preferably, the liquid-solid ratio of the ferrate raw material to the solvent in the step (1) is 2-5 mL/g.
6. The production method according to any one of claims 3 to 5, wherein the mixing in step (1) is performed under an inert gas and/or nitrogen atmosphere;
preferably, the inert gas comprises argon and/or helium;
preferably, the mixing in step (1) further comprises stirring;
preferably, the rotating speed of the stirring is 200-500 r/min;
preferably, the stirring time is 3-5 h.
7. The production method according to any one of claims 3 to 6, wherein the calcination in step (2) is performed under an ozone atmosphere;
preferably, the calcination in the step (2) comprises a temperature rise process and a constant temperature process;
preferably, the heating rate of the heating process is 3-10 ℃/min;
preferably, the end temperature of the temperature rise process is 700-900 ℃;
preferably, the constant temperature process is carried out under a mixed atmosphere of ozone and a protective gas;
preferably, the protective gas comprises argon and/or nitrogen;
preferably, the constant temperature process is carried out for 3-5 hours.
8. The method according to any one of claims 3 to 7, wherein the calcining of step (2) further comprises washing and drying;
preferably, the wash solution for washing comprises an organic solvent;
preferably, the drying temperature is 40-60 ℃;
preferably, the drying time is 2-4 h.
9. The method according to any one of claims 3 to 8, characterized by comprising the steps of:
(1) mixing an aluminum source, a ferrate raw material and an organic solvent in an inert gas atmosphere, and stirring at a rotating speed of 200-500 rpm for 3-5 hours to obtain a mixture;
(2) heating the mixture obtained in the step (1) to 700-900 ℃ at a speed of 3-10 ℃/min under an ozone atmosphere, introducing argon and/or nitrogen, calcining at a constant temperature for 3-5 h, cleaning with an organic solvent, and drying at 40-60 ℃ for 2-4 h to obtain the modified ferrate cathode material;
the particle size range of the ferrate raw material in the step (1) is 5-10 mu m; the aluminum source comprises any one of aluminum oxide, aluminum hydroxide, isopropyl aluminum oxide or aluminum salt or a combination of at least two of the aluminum oxide, the aluminum hydroxide, the isopropyl aluminum oxide or the aluminum salt; the organic solvent comprises any one of methanol, ethanol or acetone; the liquid-solid ratio of the aluminum source to the organic solvent is 35-85 mL/g; the liquid-solid ratio of the ferrate raw material to the organic solvent is 2-5 mL/g.
10. A lithium ion battery, characterized in that the modified ferrate cathode material of claim 1 or 2 is contained in the lithium ion battery.
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