CN114665087B - Three-dimensional compact rolled lithium cobaltate film material and preparation method and application thereof - Google Patents
Three-dimensional compact rolled lithium cobaltate film material and preparation method and application thereof Download PDFInfo
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- CN114665087B CN114665087B CN202011538163.7A CN202011538163A CN114665087B CN 114665087 B CN114665087 B CN 114665087B CN 202011538163 A CN202011538163 A CN 202011538163A CN 114665087 B CN114665087 B CN 114665087B
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- 239000000463 material Substances 0.000 title claims abstract description 86
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims abstract description 52
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims abstract description 52
- 230000000737 periodic effect Effects 0.000 claims abstract description 45
- 238000005096 rolling process Methods 0.000 claims abstract description 9
- 239000010405 anode material Substances 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 83
- 239000003792 electrolyte Substances 0.000 claims description 37
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 32
- 229910017052 cobalt Inorganic materials 0.000 claims description 28
- 239000010941 cobalt Substances 0.000 claims description 28
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 25
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 238000006138 lithiation reaction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000004321 preservation Methods 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 239000010409 thin film Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 8
- 150000001868 cobalt Chemical class 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- KDMCQAXHWIEEDE-UHFFFAOYSA-L cobalt(2+);7,7-dimethyloctanoate Chemical compound [Co+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O KDMCQAXHWIEEDE-UHFFFAOYSA-L 0.000 claims description 3
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000013461 design Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000004020 conductor Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000002003 electron diffraction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 239000006059 cover glass Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000002524 electron diffraction data Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- NSRBDSZKIKAZHT-UHFFFAOYSA-N tellurium zinc Chemical compound [Zn].[Te] NSRBDSZKIKAZHT-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- -1 for example Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/02—Single-crystal growth directly from the solid state by thermal treatment, e.g. strain annealing
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
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- 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
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- 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
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- 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
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Abstract
The invention discloses a structural design and a preparation method of a three-dimensional compact rolled lithium cobalt oxide film material, which is formed by densely rolling a two-dimensional lithium cobalt oxide film with uniform thickness; the two-dimensional lithium cobalt oxide film is configured to have a smooth surface, or to have a surface with nano-to-micro periodic ridge line microstructures, or to have a surface with nano-to-micro periodic ridge lines and periodic nanopore microstructures. The three-dimensional compact rolled lithium cobalt oxide film material has the characteristics of large specific surface area, regular microstructure morphology, easy size regulation and control and the like, and is a better lithium battery anode material.
Description
Technical Field
The invention relates to a structural design and a preparation method of a lithium ion battery positive electrode material, in particular to a lithium ion battery lithium cobaltate positive electrode material with a microstructure and a preparation method thereof.
Background
The three-dimensional micro-nano structure is an important direction of the development of future lithium ion batteries. The three-dimensional micro-nano structure electrode has high specific surface area compared with the block structure, and has rich pore diameters among the structures, so that the three-dimensional micro-nano structure electrode has excellent electrochemical performance. The three-dimensional micro-nano structure electrode is used for lithium battery assembly, which is beneficial to shortening the migration path of charges in the electrode, thereby improving the rate capability of the battery. Meanwhile, because lithium ions have limited embedding and extracting depths in the electrode material, the abundant pore diameters are favorable for the infiltration of electrolyte, thereby effectively utilizing the active material and achieving higher specific capacity. In addition, compared with a bulk material, the three-dimensional micro-nano structure can be more flexibly adapted to the volume change caused by the electrochemical reaction of the electrode material in the use process of the lithium battery, so that the structure is kept stable, and the safety performance of the battery is improved. Therefore, by controlling the morphology structure of the electrode material, the rate capability, specific capacity and safety performance of the battery can be effectively improved. However, the existing three-dimensional micro-nano structure is generally low in order degree, small in specific surface area and large in density, and common three-dimensional micro-nano materials are composed of carbon or oxide and the like, so that current collecting effect is poor. Therefore, there is an urgent need to provide a method for preparing a lithium ion battery positive electrode material capable of effectively controlling a micro-nano structure.
The lithium cobaltate has higher charge and discharge platform, high specific capacity and good cycle performance, so that the lithium cobaltate becomes a common lithium battery anode material. The existing methods for synthesizing the material include a solid phase reaction method, a sol-gel method, a hydrothermal method and the like, but the morphology of the lithium cobaltate prepared by the synthesis methods is usually powder particles, and the particle size distribution is difficult to control uniformly.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a three-dimensional compact rolled lithium cobalt oxide film material capable of effectively regulating and controlling a micro-nano structure and a preparation method thereof. The three-dimensional compact folded lithium cobalt oxide film material can also respectively show three characteristics of smooth surface, periodic ridge line and periodic pore surface according to different power signals, and the formed three-dimensional micro-nano structure has the characteristics of large specific surface area, regular morphology, easy regulation and control of size and the like, and is a better lithium battery anode material.
The technical scheme of the invention is as follows:
Scheme one: a compact rolled lithium cobalt oxide film material with a three-dimensional structure is formed by rolling standing two-dimensional lithium cobalt oxide films with uniform thickness; the two-dimensional lithium cobalt oxide thin film is configured to have a smooth surface, or is configured to have a surface of periodic ridge line structure, or is configured to have a surface of periodic ridge line and periodic pore structure.
As a preferable scheme, the thickness of the two-dimensional lithium cobalt oxide film is 50 nm-1 μm; the distance between adjacent two-dimensional lithium cobalt oxide films is 0.1 μm to 100 μm, preferably 0.3 μm to 10 μm.
As a preferable mode, the height of the three-dimensional structure is 10 μm to 5mm, preferably 50 μm to 2mm.
Scheme II: a positive electrode of a lithium ion battery is made of the three-dimensional compact rolled lithium cobalt oxide film material according to any one of the scheme I and the preferred scheme.
Scheme III: the method for preparing the three-dimensional compact rolled lithium cobalt oxide film material according to any one of the first scheme and the preferred scheme thereof mainly comprises the following steps:
S1, providing an electrolytic cell; regulating the temperature of electrolyte in the electrolytic cell to be near a freezing point, condensing the electrolyte, driving electrochemical deposition between the anode and the cathode in the electrolytic cell through a power signal, and carrying out electrochemical growth on the deposition in the liquid electrolyte from the cathode to the anode to obtain a three-dimensional compact rolled film material of the metal cobalt after the growth is finished; the electrolyte in the electrolytic cell is cobalt salt, and the anode material of the electrode is metallic cobalt; the power supply signal is a constant signal or a periodic signal;
s2, carrying out high-temperature oxidation on the three-dimensional compact rolled film material of the metal cobalt as a precursor to prepare a three-dimensional compact rolled cobaltosic oxide film material;
and S3, carrying out high-temperature lithiation by taking the cobaltosic oxide film material as a precursor to prepare the three-dimensional compact rolled lithium cobaltate film material.
As a preferable mode, when the power supply signal is a constant signal, the two-dimensional lithium cobalt oxide thin film is configured to have a smooth surface; when the power supply signal is a periodic signal, the two-dimensional lithium cobalt oxide film is configured as a surface having a periodic ridge line structure or as a surface having a periodic ridge line and a periodic pore structure, and the period of the ridge line structure and/or the pore structure and the width and height of the ridge line structure are adjusted by the frequency and amplitude of the periodic signal.
As a preferable scheme, the cobalt salt is one or a mixture of at least two of cobalt naphthenate, cobalt stearate, cobalt neodecanoate and CoF 2、CoSO4、CoCl2、Co(NO3)2; the concentration of the cobalt salt is 0.01-1 mol/L.
As a preferred scheme, the electrolytic cell adopts a sandwich structure and comprises an upper substrate, a lower substrate, and an electrode and electrolyte arranged between the upper substrate and the lower substrate.
As a preferable scheme, the temperature of the electrolyte can be adjusted by a temperature control device; the temperature control device is a constant-temperature water bath system; the electrolytic cell is placed in a heat preservation chamber, the heat preservation chamber is connected with a constant temperature water bath system, and the electrode is connected with a signal generator; the temperature of the electrolyte is regulated by regulating the temperature of the constant-temperature water bath system.
As a preferred solution, the step S2 specifically includes: and (3) placing the three-dimensional compact coiled sample of the metallic cobalt in a tube furnace in an oxygen atmosphere for high-temperature oxidation to synthesize the cubic cobaltosic oxide polycrystalline material.
As a preferred solution, the step S3 specifically includes: dropwise adding a solution of lithium carbonate on the three-dimensional compact rolled cobaltosic oxide film material; then carrying out high-temperature lithiation in a tube furnace in an oxygen atmosphere, and synthesizing a rhombohedral lithium cobalt oxide polycrystalline material by high-temperature lithium synthesis; the concentration of the solution of lithium carbonate is 0.5-1mol/L.
The invention has the following beneficial effects:
(1) The three-dimensional compact rolling film material of the cobalt, the cobaltosic oxide and the lithium cobaltate is prepared by adopting an electrochemical method, the finally formed three-dimensional compact rolling film material of the lithium cobaltate consists of a standing two-dimensional lithium cobaltate film with uniform thickness distribution, and the film can have three characteristics of smooth surface, periodic ridge line surface and periodic pore surface, and the formed three-dimensional micro-nano structure has the characteristics of large specific surface area, regular morphology, easy size regulation and the like.
(2) The three-dimensional compact rolled lithium cobaltate film material prepared by the invention has the advantages of regular and orderly micro-nano structure, easy control and great potential in the aspects of rate capability, specific capacity, safety performance and the like in lithium ion battery application.
(3) According to the preparation method of the three-dimensional compact rolled lithium cobalt oxide film material, parameters such as the surface morphology, the space density and the specific size of the three-dimensional compact rolled lithium cobalt oxide film material can be adjusted by changing the concentration and the thickness of an initial electrolyte, the parameters of a power signal and the like.
(4) The three-dimensional compact rolled lithium cobalt oxide film material adopted by the invention has common raw materials, low cost, high efficiency, low energy consumption, simple operation and easy adjustment, realizes the nano-scale processing precision, and has high reliability and repeatability.
Drawings
FIG. 1 is a schematic diagram of an apparatus for preparing a three-dimensional compact roll-up of metallic cobalt film material. Wherein ① and ⑤ are cathode and anode; ② Is a lower substrate, and can be selected as a silicon wafer; ③ Is an electrolyte; ④ Is an upper substrate, and a cover glass can be selected; ⑥ Is a glass observation window; ⑦ Is a heat preservation chamber.
Fig. 2 is an electron microscopy image of a typical three-dimensional dense rolled thin film material of metallic cobalt grown electrochemically.
FIG. 3 is an enlarged view of a typical morphology of a three-dimensional densely rolled film material prepared using different types of power signals as a driving power source. Wherein: FIG. 3a is a three-dimensional metal film of uniform, relatively smooth thickness grown using a constant power signal; FIG. 3b is a thin film material having pores, periodic ridges, obtained by electrochemical growth using periodic signals; fig. 3c is a void-free, thin film material with periodic ridges, obtained by electrochemical growth using a periodic signal.
FIG. 4 is a graph of morphology contrast and corresponding transmission electron diffraction patterns of three-dimensional densely rolled film materials before and after high temperature oxidation and lithiation. Wherein fig. 4a is a three-dimensional dense roll of metallic cobalt film material; FIG. 4b is a three-dimensional dense roll of tricobalt tetraoxide film material at the same location after oxidation; FIG. 4c is a three-dimensional dense roll of lithium cobaltate film material at the same location after lithiation; FIG. 4d is a transmission electron diffraction spectrum of the sample of FIG. 4a under the same conditions, the diffraction pattern corresponding to the polycrystalline metallic cobalt of the close-packed hexagonal structure; FIG. 4e is a transmission electron diffraction spectrum of the sample of FIG. 4b under the same conditions, the diffraction pattern corresponding to polycrystalline tricobalt tetraoxide of cubic structure; fig. 4f is a transmission electron diffraction spectrum of the sample of fig. 4c under the same conditions, the diffraction pattern of which corresponds to that of the rhombohedral structure lithium cobaltate polycrystalline material.
Detailed Description
The invention discloses a structural design and a preparation method of a three-dimensional compact rolled lithium cobalt oxide film material and application of a lithium ion battery based on the three-dimensional compact rolled lithium cobalt oxide film material. The three-dimensional compact rolling lithium cobalt oxide film material is a three-dimensional structure formed by standing lithium cobalt oxide films with uniform thickness in a three-dimensional space compact rolling manner. The preparation method of the lithium cobalt oxide film three-dimensional compact winding material adopts an electrochemical method. The lithium cobaltate film three-dimensional compact winding material disclosed by the invention can be used as an anode active material of a lithium ion secondary battery.
Specifically, the embodiment provides a preparation method of a three-dimensional compact rolled lithium cobalt oxide film material, which mainly comprises the following three stages, wherein the specific scheme of each stage is as follows:
The first stage: preparing a three-dimensional compact rolled film material of the metal cobalt. This stage mainly comprises the following steps:
s1: and (3) configuring an electrolytic cell, and then placing the configured electrolytic cell in a thermal insulation growth chamber.
The electrolytic cell is a sandwich structure built by adopting a planar substrate as shown in fig. 1, the lower substrate can be an insulating substrate such as a glass sheet, a silicon wafer and the like, electrolyte with a certain thickness is coated on the surface of the lower substrate, at the moment, the electrodes are generally horizontally arranged and are in line contact with the lower substrate along the length direction, the surface of the electrolyte is an upper substrate, and a cover glass sheet can be covered.
The electrolyte arranged in the electrolytic cell can be one or more of cobalt naphthenate, cobalt stearate, cobalt neodecanoate, coF 2、CoSO4、Co(NO3)2、CoCl2 or other cobalt salts, and the concentration is 0.01 mol/L-1 mol/L. The thickness of the electrolyte also generally determines the maximum width of the three-dimensional structure. In the two electrodes, the anode is made of cobalt material, for example, cobalt sheets or cobalt wires can be selected as the anode; the cathode may be a metallic conductor, a non-metallic conductor, or a composite material formed of any metallic conductor and/or non-metallic conductor, for example, metallic silver, copper, cobalt, graphene, or the like may be selected. The distance between the electrodes generally determines the maximum limit of the lateral growth dimension of the three-dimensional structure. The other ends of the two electrodes are connected with a signal generator.
Wherein, the temperature control device can be a constant temperature water bath system. The liquid of the constant temperature water bath system is a refrigerant, is connected with the heat preservation chamber, is mainly used for adjusting the temperature in the heat preservation chamber, and can be used for providing a temperature environment close to the freezing point of electrolyte. The heat preservation cover is provided with a glass observation window, and the change in the heat preservation growth chamber can be observed through the glass observation window.
S2: and setting the temperature of the constant-temperature water bath system to be minus, starting the system to cool, and enabling the electrolyte to be coagulated when the temperature of the constant-temperature water bath system and the temperature preservation chamber reach a stable state.
S3: and setting a driving power supply signal through a signal generator, and driving electrochemical deposition to occur between electrodes in the electrolyte, wherein the deposition electrochemically grows from a cathode to an anode in the electrolyte. A power signal is applied between the cathode and the anode, a reduction reaction occurs at the cathode, and cobalt ions in the electrolyte are reduced into metal atoms so as to be deposited; an oxidation reaction occurs at the anode, and metallic cobalt is oxidized to cobalt ions into the electrolyte. The power signal may be a constant signal or a periodic signal. With a constant signal, the surface of the two-dimensional film of the final deposit can be made smoother. When a periodic signal is used, the periodic ridge line structure is represented on the final formed morphology, or the periodic ridge line and the periodic pore structure are added, and particularly, the period of the ridge line structure and/or the pore structure and the width and the height of the ridge line structure can be adjusted through the frequency and the amplitude of the periodic signal.
S4: and when the sediment growth is finished, cutting off power supply signals at two ends of the electrode to prepare the three-dimensional compact rolled and folded sample of the metal cobalt. Raising the temperature of the constant-temperature water bath system to room temperature, completely melting the electrolyte to be liquid, taking out the sample, removing the residual electrolyte solution, and drying for later use.
And a second stage: and (3) taking the three-dimensional compact rolled and stacked sample of the metal cobalt as a precursor, and carrying out high-temperature oxidation by using a tube furnace to prepare the three-dimensional compact rolled and stacked cobaltosic oxide film material.
Specifically, the tubular furnace is subjected to high-temperature oxidation in an atmosphere filled with oxygen, and the transmission electron microscope characterization shows that the step of high-temperature oxidation synthesizes the cobaltosic oxide polycrystalline material of the cubic crystal system.
And a third stage: and taking the tricobalt tetraoxide three-dimensional compact rolled and folded sample as a precursor, and carrying out high-temperature lithiation by utilizing a tube furnace to prepare the three-dimensional compact rolled and folded lithium cobalt oxide film material.
Specifically, the solution of lithium carbonate with the concentration of 0.5-1mol/L can be dripped on the prepared three-dimensional compact rolled cobaltosic oxide material; and then high-temperature reaction is carried out in a tube furnace filled with oxygen. Transmission electron microscope characterization shows that the step of high-temperature lithiation synthesizes the rhombohedral lithium cobalt oxide polycrystalline material.
Thus, the preparation of the target three-dimensional compact rolled lithium cobalt oxide film material is completed.
Referring to fig. 2 to 3, a three-dimensional densely-rolled lithium cobaltate thin film material is further disclosed in the embodiment, wherein the three-dimensional densely-rolled lithium cobaltate thin film material is a three-dimensional structure formed by densely rolling standing two-dimensional thin films with uniform thickness, and the total height (seen along the growth direction) of the three-dimensional densely-rolled thin film material is about 10 micrometers to 5 millimeters. Wherein the thickness of the two-dimensional film is uniform and is about 50 nanometers to 1 micrometer, and the distance between adjacent two-dimensional films is about 0.1 micrometer to 100 micrometers, preferably 0.3 micrometer to 10 micrometers. The surface of the two-dimensional film may be smooth, have periodic ridge line structures, or have both periodic ridge lines and periodic pore structures. The three-dimensional compact rolled lithium cobalt oxide film material can be prepared by the method, but is not limited to the method.
In the preparation process of the three-dimensional compact folded lithium cobalt oxide film material, the two-dimensional film can be provided with a smooth surface, a periodic ridge line surface or a surface with a periodic ridge line and periodic pore structure by controlling the type of a driving power signal, such as a constant signal or a periodic signal, of electrochemical growth, and the width, the height and the period of the ridge line and the size and the period of the pores can be adjusted by the frequency and the amplitude of the power signal.
The invention will be further described with reference to specific examples and figures.
Example 1: a three-dimensional compact roll-laminated film material of lithium cobaltate.
Preparing 0.02mol/L cobalt chloride solution as electrolyte, selecting a silicon wafer substrate as a lower substrate, adopting a cobalt sheet as an electrode, and placing the cobalt sheet on the silicon wafer substrate. The electrolyte is dripped on a silicon wafer substrate, a cover glass is covered on the electrolyte as an upper substrate, and the electrolyte and the upper substrate are placed in the middle of a heat preservation chamber. And cooling by using a constant-temperature water bath to coagulate the electrolyte. Thereafter, a periodic power signal is applied across the electrodes for electrochemical growth. And after the growth of the sediment is finished, taking out the sample, removing the residual electrolyte solution, and drying for later use. FIG. 2 is a sample of a three-dimensional compact rolled film material of metallic cobalt obtained under the condition, wherein the macroscopic size of the sample reaches millimeter magnitude, and the two-dimensional film has uniform thickness and shows a regular three-dimensional structure; wherein the two-dimensional film has a smooth surface and a thickness of about 100nm.
The three-dimensional compact coiled film material of the metal cobalt is placed in the center of a tube furnace, oxygen is introduced, and high-temperature oxidation is carried out. Transmission electron microscope characterization shows that the step of high-temperature oxidation synthesizes the cobaltosic oxide polycrystalline material of the cubic crystal system. Fig. 4a and 4b are morphology comparison graphs of the same sample before and after oxidation, and fig. 4d and 4e below are transmission electron diffraction patterns of the sample under the same conditions, respectively, showing that the sample before and after oxidation is a polycrystalline cobalt and a cobaltosic oxide material of hexagonal system and cubic system, respectively.
And taking the three-dimensional compact rolled tricobalt tetraoxide sample as a precursor, dripping a solution of lithium carbonate on the prepared three-dimensional compact rolled tricobalt tetraoxide material, completely soaking the sample, placing the sample in a tube furnace, introducing oxygen, and carrying out high-temperature lithiation to fully react. Fig. 4b and 4c are morphology comparison diagrams of the same sample before and after lithiation, and fig. 4f is a transmission electron diffraction diagram of the sample after lithiation, and the result shows that the high-temperature lithiation in this step synthesizes a rhombohedral lithium cobalt oxide polycrystalline material.
Example 2: a three-dimensional compact roll-laminated film material of lithium cobaltate.
Preparing a cobalt sulfate solution with the concentration of 0.01mol/L as an electrolyte, building an electrolytic cell by using a mica sheet substrate, adopting cobalt wires with the diameter of 0.1mm as electrodes, and placing the cobalt wires on the mica sheet substrate. The electrolyte is dripped on a mica sheet substrate, a cover slip is covered on the electrolyte, and the electrolyte and the cover slip are placed in the middle of a heat preservation chamber. And cooling by using a constant-temperature water bath to coagulate the electrolyte. Thereafter, a periodic power signal is applied across the electrodes for electrochemical growth. And after the growth of the sediment is finished, taking out the sample, removing the residual electrolyte solution, and drying for later use. Fig. 3b shows a three-dimensional compact rolled film material of metallic cobalt obtained under the condition, wherein the surface of the two-dimensional film has a pore structure and a periodic ridge line structure, and the thickness is uniform.
The three-dimensional compact coiled film material of the metal cobalt is placed in the center of a tube furnace, oxygen is introduced, and high-temperature oxidation is carried out. As in example 1, a cubic tricobalt tetraoxide polycrystalline material was synthesized by high-temperature oxidation.
And (3) putting the three-dimensional compact rolled and folded cobaltosic oxide sample serving as a precursor into a tube furnace, dripping a solution of lithium carbonate on the prepared three-dimensional compact rolled and folded cobaltosic oxide material, introducing oxygen, and carrying out high-temperature lithiation. As in example 1, this step was lithiated at high temperature to synthesize a rhombohedral lithium cobalt oxide polycrystalline material.
Finally, it should be noted that although the embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments and application fields, and the above-described embodiments are merely illustrative, and not restrictive. Those skilled in the art, having the benefit of this disclosure, may effect numerous forms of the invention without departing from the scope of the invention as claimed.
Claims (13)
1. A method for preparing a three-dimensional compact rolled lithium cobalt oxide film material, which is characterized by comprising the following steps:
S1, providing an electrolytic cell; regulating the temperature of electrolyte in the electrolytic cell to be near a freezing point, condensing the electrolyte, driving electrochemical deposition between the anode and the cathode in the electrolytic cell through a power signal, and carrying out electrochemical growth on the deposit in the electrolyte from the cathode to the anode to obtain a three-dimensional compact rolled film material of the metallic cobalt after the growth is finished; the electrolyte in the electrolytic cell is cobalt salt, and the anode material of the electrode is metallic cobalt; the power supply signal is a constant signal or a periodic signal;
s2, carrying out high-temperature oxidation on the three-dimensional compact rolled film material of the metal cobalt as a precursor to prepare a three-dimensional compact rolled cobaltosic oxide film material;
s3, carrying out high-temperature lithiation by taking the cobaltosic oxide film material as a precursor to prepare a three-dimensional compact rolled lithium cobaltate film material;
The three-dimensional compact rolled lithium cobalt oxide film material is of a three-dimensional structure, and the three-dimensional structure is formed by standing two-dimensional lithium cobalt oxide films with uniform thickness in a compact rolling mode.
2. The method of claim 1, wherein the two-dimensional lithium cobalt oxide film is configured to have a smooth surface when the power signal is a constant signal; when the power supply signal is a periodic signal, the two-dimensional lithium cobalt oxide film is configured as a surface having a periodic ridge line structure or as a surface having a periodic ridge line and a periodic pore structure, and the period of the ridge line structure and/or the pore structure and the width and height of the ridge line structure are adjusted by the frequency and amplitude of the periodic signal.
3. The method of claim 1, wherein the cobalt salt is one or a mixture of at least two of cobalt naphthenate, cobalt stearate, cobalt neodecanoate, coF 2、CoSO4、CoCl2、Co(NO3)2; the concentration of the cobalt salt is 0.01-1 mol/L.
4. The method of claim 1, wherein the electrolytic cell is in a sandwich configuration comprising an upper substrate, a lower substrate, and an electrode and electrolyte disposed between the upper substrate and the lower substrate.
5. The method of claim 1, wherein the temperature of the electrolyte is adjusted by a temperature control device; the temperature control device is a constant-temperature water bath system; the electrolytic cell is placed in a heat preservation chamber, the heat preservation chamber is connected with a constant temperature water bath system, and the electrode is connected with a signal generator; the temperature of the electrolyte is regulated by regulating the temperature of the constant-temperature water bath system.
6. The method according to claim 1, wherein the step S2 specifically includes: placing the three-dimensional compact coiled sample of the metal cobalt in a tubular furnace in an oxygen atmosphere for high-temperature oxidation, and synthesizing a cobaltosic oxide polycrystalline material of a cubic crystal system after the high-temperature oxidation;
The step S3 specifically includes: dropwise adding a solution of lithium carbonate on the three-dimensional compact rolled cobaltosic oxide film material; then carrying out high-temperature lithiation in a tube furnace in an oxygen atmosphere to synthesize a rhombohedral lithium cobalt oxide polycrystalline material; the concentration of the solution of lithium carbonate is 0.5-1mol/L.
7. A three-dimensional compact roll-up lithium cobalt oxide film material, characterized in that the three-dimensional compact roll-up lithium cobalt oxide film material is prepared by the method for preparing the three-dimensional compact roll-up lithium cobalt oxide film material according to any one of claims 1 to 6.
8. The three-dimensional densely-rolled lithium cobalt oxide film material according to claim 7, wherein the three-dimensional densely-rolled lithium cobalt oxide film material has a three-dimensional structure formed by densely rolling standing two-dimensional lithium cobalt oxide films with uniform thickness; the two-dimensional lithium cobalt oxide thin film is configured to have a smooth surface, or is configured to have a surface of periodic ridge line structure, or is configured to have a surface of periodic ridge line and periodic pore structure.
9. The three-dimensional compact rolled lithium cobalt oxide film material according to claim 8, wherein the thickness of the two-dimensional lithium cobalt oxide film is 50 nm-1 um; the distance between adjacent two-dimensional lithium cobalt oxide films is 0.1 um-100 um.
10. The three-dimensional densely-rolled lithium cobalt oxide film material according to claim 9, wherein the distance between adjacent two-dimensional lithium cobalt oxide films is 0.3-10 um.
11. The three-dimensional densely-rolled lithium cobalt oxide film material according to claim 8, wherein the height of the three-dimensional structure is 10 um-5 mm.
12. The three-dimensional compact roll-up lithium cobaltate film material of claim 11, wherein the three-dimensional structure has a height of 50um to 2mm.
13. A lithium ion battery, characterized in that the positive electrode is made of the three-dimensional compact rolled lithium cobalt oxide film material according to any one of claims 7 to 12.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3455738A (en) * | 1965-12-01 | 1969-07-15 | Samuel Ruben | Method of making rechargeable cell having ionically permeable gel and electrode therefor |
| CA2308346A1 (en) * | 1999-05-14 | 2000-11-14 | Mitsubishi Cable Industries, Ltd. | Positive electrode active material, positive electrode active material composition and lithium ion secondary battery |
| WO2001091211A1 (en) * | 2000-05-24 | 2001-11-29 | Mitsubishi Cable Industries, Ltd. | Lithium secondary cell and positive electrode active material, positive plate, and method for manufacturing them |
| CA2450978A1 (en) * | 2001-11-22 | 2003-06-05 | Francois Cardarelli | A method for electrowinning of titanium metal or alloy from titanium oxide containing compound in the liquid state |
| KR20090012143A (en) * | 2007-07-26 | 2009-02-02 | 소니 가부시끼 가이샤 | Anode and battery |
| WO2014050872A1 (en) * | 2012-09-28 | 2014-04-03 | ダイキン工業株式会社 | Electrolyte solution, electrochemical device, lithium battery, and module |
| WO2017204984A1 (en) * | 2016-05-27 | 2017-11-30 | The Regents Of The University Of California | Electrochemical energy storage device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6907805B2 (en) * | 2017-08-17 | 2021-07-21 | セイコーエプソン株式会社 | Complexes, lithium batteries, composite manufacturing methods, lithium battery manufacturing methods, electronic devices |
| US11462729B2 (en) * | 2018-04-12 | 2022-10-04 | Massachusetts Institute Of Technology | Electrodes comprising composite mixtures and related devices and methods |
-
2020
- 2020-12-23 CN CN202011538163.7A patent/CN114665087B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3455738A (en) * | 1965-12-01 | 1969-07-15 | Samuel Ruben | Method of making rechargeable cell having ionically permeable gel and electrode therefor |
| CA2308346A1 (en) * | 1999-05-14 | 2000-11-14 | Mitsubishi Cable Industries, Ltd. | Positive electrode active material, positive electrode active material composition and lithium ion secondary battery |
| WO2001091211A1 (en) * | 2000-05-24 | 2001-11-29 | Mitsubishi Cable Industries, Ltd. | Lithium secondary cell and positive electrode active material, positive plate, and method for manufacturing them |
| CA2450978A1 (en) * | 2001-11-22 | 2003-06-05 | Francois Cardarelli | A method for electrowinning of titanium metal or alloy from titanium oxide containing compound in the liquid state |
| KR20090012143A (en) * | 2007-07-26 | 2009-02-02 | 소니 가부시끼 가이샤 | Anode and battery |
| WO2014050872A1 (en) * | 2012-09-28 | 2014-04-03 | ダイキン工業株式会社 | Electrolyte solution, electrochemical device, lithium battery, and module |
| WO2017204984A1 (en) * | 2016-05-27 | 2017-11-30 | The Regents Of The University Of California | Electrochemical energy storage device |
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