CN114665087A - Three-dimensional compact roll-up lithium cobaltate thin film material and preparation method and application thereof - Google Patents
Three-dimensional compact roll-up lithium cobaltate thin film material and preparation method and application thereof Download PDFInfo
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- CN114665087A CN114665087A CN202011538163.7A CN202011538163A CN114665087A CN 114665087 A CN114665087 A CN 114665087A CN 202011538163 A CN202011538163 A CN 202011538163A CN 114665087 A CN114665087 A CN 114665087A
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- 239000000463 material Substances 0.000 title claims abstract description 80
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 66
- 239000010409 thin film Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 230000000737 periodic effect Effects 0.000 claims abstract description 45
- 239000010408 film Substances 0.000 claims abstract description 35
- 238000005096 rolling process Methods 0.000 claims abstract description 30
- 239000010405 anode material Substances 0.000 claims abstract description 7
- 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 44
- 239000003792 electrolyte Substances 0.000 claims description 34
- 239000000758 substrate Substances 0.000 claims description 29
- 239000010941 cobalt Substances 0.000 claims description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 24
- 229910017052 cobalt Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000006138 lithiation reaction Methods 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 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
- 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
- 239000013078 crystal Substances 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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt(II) nitrate Inorganic materials [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- 229910021582 Cobalt(II) fluoride 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
- 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 group 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000006059 cover glass Substances 0.000 description 6
- 238000002524 electron diffraction data Methods 0.000 description 6
- 239000010445 mica Substances 0.000 description 5
- 229910052618 mica group Inorganic materials 0.000 description 5
- 239000004020 conductor Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000001276 controlling effect Effects 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
- 239000013049 sediment Substances 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
- 238000012512 characterization method Methods 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
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 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
- 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 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
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 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
- 238000010586 diagram Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 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
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007774 positive electrode material Substances 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
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 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
- 238000012876 topography Methods 0.000 description 1
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- 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
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- 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
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- 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
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- 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
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The invention discloses a structure design and a preparation method of a three-dimensional compact rolled lithium cobaltate film material, wherein the material is formed by compactly rolling a two-dimensional lithium cobaltate film with uniform thickness; the two-dimensional lithium cobaltate thin film is configured to have a smooth surface, or configured to have a surface with a nano-to-micro periodic ridge line microstructure, or configured to have a surface with a nano-to-micro periodic ridge line and a periodic nanoporous microstructure. The three-dimensional compact rolled lithium cobaltate 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 structure design and a preparation method of a lithium ion battery anode material, in particular to a lithium ion battery lithium cobaltate anode material with a microstructure and a preparation method thereof.
Background
The three-dimensional micro-nano structure is an important direction for the development of the lithium ion battery in the future. Compared with a block structure, the three-dimensional micro-nano structure has a higher specific surface area, and the structures have rich apertures, so that the three-dimensional micro-nano structure electrode has excellent electrochemical performance. The lithium battery is assembled by using the three-dimensional micro-nano structure electrode, so that the migration path of charges in the electrode is favorably shortened, and the rate capability of the battery is improved. Meanwhile, because lithium ions have limited insertion and extraction depths in the electrode material, the abundant pore diameters are beneficial to the infiltration of electrolyte, thereby effectively utilizing active materials and achieving higher specific capacity. In addition, compared with a block 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, the rate capability, specific capacity and safety performance of the battery can be effectively improved by controlling the morphology structure of the electrode material. However, the current three-dimensional micro-nano structure is generally low in order degree, small in specific surface area and high in density, a common three-dimensional micro-nano material is composed of carbon or oxide and the like, and the current collecting effect is poor. Therefore, a preparation method of the lithium ion battery cathode material capable of effectively controlling the micro-nano structure is urgently needed.
Lithium cobaltate has a higher charge-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 comprise a solid-phase reaction method, a sol-gel method, a hydrothermal method and the like, but the shape of 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 thin film material capable of effectively regulating a micro-nano structure and a preparation method thereof. The three-dimensional compact rolled lithium cobaltate thin film material can respectively present three characteristics of a smooth surface, a surface with periodic ridge lines and periodic pores according to different power signals, and the formed three-dimensional micro-nano structure has the characteristics of large specific surface area, regular appearance, easy size regulation and control and the like, and is a better lithium battery anode material.
The technical scheme of the invention is as follows:
the first scheme is as follows: a compact roll-up lithium cobaltate thin film material with a three-dimensional structure is formed by rolling up a standing two-dimensional lithium cobaltate thin film with uniform thickness; the two-dimensional lithium cobaltate thin film is configured to have a smooth surface, or a surface having a periodic ridge line structure, or a surface having a periodic ridge line and a periodic pore structure.
Preferably, the thickness of the two-dimensional lithium cobaltate film is 50 nm-1 μm; the pitch between adjacent two-dimensional lithium cobaltate thin films is 0.1 to 100 μm, preferably 0.3 to 10 μm.
Preferably, the height of the three-dimensional structure is 10 μm to 5mm, preferably 50 μm to 2 mm.
Scheme II: a lithium ion battery, wherein the positive electrode is made of the three-dimensional compact roll-stacked lithium cobaltate thin film material according to any one of the first scheme and the preferred scheme.
The third scheme is as follows: the method for preparing the three-dimensional compact roll-to-roll lithium cobaltate thin film material according to the first embodiment and the preferred embodiments thereof mainly comprises the following steps:
s1, providing an electrolytic cell; adjusting the temperature of electrolyte in the electrolytic cell to be near the freezing point to condense the electrolyte, then driving electrochemical deposition to occur between a cathode and an anode in the electrolytic cell through a power supply signal, carrying out electrochemical growth on sediments from a cathode to an anode in the liquid electrolyte, and preparing a three-dimensional compact rolling 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 metal cobalt; the power supply signal is a constant signal or a periodic signal;
s2, performing high-temperature oxidation by using the three-dimensional compact rolling and folding film material of the metal cobalt as a precursor to prepare a three-dimensional compact rolling and folding cobaltosic oxide film material;
and S3, carrying out high-temperature lithiation by taking the cobaltosic oxide thin film material as a precursor to prepare the three-dimensional compact rolling lithium cobaltate thin film material.
As a preferable mode, when the power supply signal is a constant signal, the two-dimensional lithium cobaltate thin film is configured to have a smooth surface; when the power supply signal is a periodic signal, the two-dimensional lithium cobaltate thin film is constructed to be a surface with a periodic ridge line structure or a surface with 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 the height of the ridge line structure are adjusted through the frequency and the amplitude of the periodic signal.
Preferably, the cobalt salt is cobalt naphthenate, cobalt stearate, cobalt neodecanoate, CoF2、CoSO4、CoCl2、Co(NO3)2One or a mixture of at least two of them; the concentration of the cobalt salt is 0.01-1 mol/L.
Preferably, the electrolytic cell is of a sandwich structure and comprises an upper substrate, a lower substrate, and an electrode and an electrolyte which are arranged between the upper substrate and the lower substrate.
As a preferred 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 adjusted by adjusting the temperature of the constant-temperature water bath system.
As a preferable scheme, the step S2 specifically includes: and (3) placing the three-dimensional compact rolling sample of the metal cobalt in a tubular furnace in an oxygen atmosphere for high-temperature oxidation to synthesize the cubic cobaltosic oxide polycrystalline material.
As a preferable scheme, the step S3 specifically includes: dropwise adding a lithium carbonate solution on the three-dimensional compact rolling cobaltosic oxide film material; then carrying out high-temperature lithiation in a tubular furnace in an oxygen atmosphere, and synthesizing a lithium cobaltate polycrystalline material of a rhombohedral crystal system through high-temperature lithiation; the concentration of the lithium carbonate solution is 0.5-1 mol/L.
The invention has the following beneficial effects:
(1) the three-dimensional compact rolled and folded thin film material of metal cobalt, cobaltosic oxide and lithium cobaltate is prepared by adopting an electrochemical method, the finally formed three-dimensional compact rolled and folded lithium cobaltate thin film material consists of a two-dimensional lithium cobaltate thin film which is standing and uniform in thickness distribution, the thin film can have three characteristics of a smooth surface, a surface of a periodic ridge line and a surface of a periodic pore, and the formed three-dimensional micro-nano structure has the characteristics of large specific surface area, regular appearance, easiness in size regulation and the like.
(2) The three-dimensional compact folded lithium cobaltate film material prepared by the invention has regular and ordered micro-nano structure, is easy to control, and has greater potential in the aspects of rate capability, specific capacity, safety performance and the like in the application of lithium ion batteries.
(3) According to the preparation method of the three-dimensional compact rolled lithium cobaltate thin film material, parameters such as the surface appearance, the space density and the specific size of the three-dimensional compact rolled lithium cobaltate thin film material can be adjusted by changing the concentration and the thickness of the initial electrolyte, the parameters of a power supply signal and the like.
(4) The preparation method of the three-dimensional compact rolled lithium cobaltate thin film material has the advantages of common raw materials, low cost, high efficiency, low energy consumption, simple operation and easy adjustment, and realizes the nano-scale processing precision and high reliability and repeatability.
Drawings
FIG. 1 is a schematic diagram of an apparatus for preparing a three-dimensional dense rolling and laminating film material of metal cobalt. Wherein, the first and the fifth are a cathode and an anode; a lower substrate which can be selected as a silicon wafer; ③ is an electrolyte; fourthly, an upper substrate can be selected, and a cover glass can be selected; sixthly, a glass observation window; and the heat preservation chamber.
Fig. 2 is an electron microscope picture of a three-dimensional dense roll-up thin film material of typical metallic cobalt obtained by electrochemical growth.
FIG. 3 is an enlarged view of a typical topography of a three-dimensional densely-rolled thin-film material prepared using different types of power signals as driving power sources. Wherein: FIG. 3a is a three-dimensional metal film grown using a constant power signal and having a uniform, relatively smooth thickness; FIG. 3b is a thin film material with voids, periodic ridges that is electrochemically grown using a periodic signal; figure 3c is a pore-free, periodic ridgeline-containing thin film material obtained by electrochemical growth using a periodic signal.
FIG. 4 is a comparison graph of the morphology of the three-dimensional densely rolled thin film material before and after high temperature oxidation and lithiation and the corresponding transmission electron diffraction pattern. Wherein FIG. 4a is a three-dimensional dense roll-up of a thin film material of metallic cobalt; FIG. 4b is the same position of the cobaltosic oxide three-dimensional dense roll-stacked thin film material after oxidation; FIG. 4c is a three-dimensional densely rolled thin film material of lithium cobaltate at the same location after lithiation; FIG. 4d is a transmission electron diffraction pattern of the sample of FIG. 4a under the same conditions, which corresponds to the polycrystalline metallic cobalt having a close-packed hexagonal structure; FIG. 4e is the transmission electron diffraction pattern of the sample of FIG. 4b under the same conditions, which corresponds to polycrystalline cobaltosic oxide having a cubic structure; FIG. 4f is a transmission electron diffraction pattern of the sample of FIG. 4c under the same conditions, which corresponds to the rhombohedral crystal structure of the lithium cobaltate polycrystalline material.
Detailed Description
The invention discloses a structure design and a preparation method of a three-dimensional compact rolled lithium cobaltate film material, and an application of a lithium ion battery based on the three-dimensional compact rolled lithium cobaltate film material. The three-dimensional compact rolled lithium cobaltate film material is a three-dimensional structure formed by standing lithium cobaltate films with uniform thickness and compact rolling in a three-dimensional space. The preparation method of the three-dimensional compact roll-up material of the lithium cobaltate film adopts an electrochemical method. The lithium cobaltate film three-dimensional compact rolling material disclosed by the invention can be used as a positive electrode active material of a lithium ion secondary battery.
Specifically, the embodiment provides a preparation method of a three-dimensional dense roll-stacked lithium cobaltate thin film material, which mainly comprises the following three stages, and the specific scheme of each stage is as follows:
the first stage is as follows: preparing the three-dimensional compact rolling film material of the metal cobalt. The stage mainly comprises the following steps:
s1: and (3) configuring an electrolytic cell, and then placing the configured electrolytic cell in a heat-preservation growth chamber.
The electrolytic cell is of 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 and a silicon wafer, electrolyte with a certain thickness is coated on the surface of the lower substrate, the electrodes are usually arranged in the horizontal direction at the moment 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 on the surface of the electrolyte.
The electrolyte in the electrolytic cell can be cobalt naphthenate, cobalt stearate, cobalt neodecanoate, CoF2、CoSO4、Co(NO3)2、CoCl2Or one or more of 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 sheet or cobalt wire can be selected as the anode; the cathode may be a metal conductor, a non-metal conductor, or a composite material formed of any metal conductor and/or non-metal conductor, such as silver, copper, cobalt, graphene, etc. The distance between the electrodes generally determines the maximum limit of the lateral growth dimension of the three-dimensional volumetric structure. The other ends of the two electrodes are connected with a signal generator.
Wherein, the temperature control device can select 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 the 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 (3) setting the temperature of the constant-temperature water bath system to be below zero, starting the system to cool, and allowing the temperature of the constant-temperature water bath system and the temperature of the heat preservation chamber to reach a stable state so as to condense the electrolyte.
S3: and setting a driving power supply signal through the signal generator to drive electrochemical deposition to occur between electrodes in the electrolyte, and performing electrochemical growth of deposits from the cathode to the anode in the electrolyte. A power supply signal is applied between the cathode and the anode, a reduction reaction is carried out at the cathode, and cobalt ions in the electrolyte are reduced into metal atoms to be deposited; an oxidation reaction occurs at the anode, and the metal cobalt is oxidized into cobalt ions entering the electrolyte. The power supply signal may be a constant signal or may be a periodic signal component. With a constant signal, the surface of the two-dimensional film of the final deposit can be made relatively smooth. When a periodic signal is used, the finally formed morphology shows a periodic ridge line structure or a periodic ridge line plus a periodic pore structure, 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 growth of the deposit is finished, cutting off power supply signals at two ends of the electrode to prepare a three-dimensional compact rolling sample of the metal cobalt. And raising the temperature of the constant-temperature water bath system to room temperature to completely melt 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 a three-dimensional compact rolling sample of the metal cobalt as a precursor, and performing high-temperature oxidation by using a tubular furnace to prepare the three-dimensional compact rolling cobaltosic oxide film material.
Specifically, the tubular furnace is subjected to high-temperature oxidation in an oxygen-filled atmosphere, and transmission electron microscope representation shows that the cobaltosic oxide polycrystalline material of a cubic system is synthesized by the high-temperature oxidation in the step.
And a third stage: and (3) taking a cobaltosic oxide three-dimensional compact roll-stacked sample as a precursor, and carrying out high-temperature lithiation by using a tube furnace to prepare the three-dimensional compact roll-stacked lithium cobaltate thin film material.
Specifically, a lithium carbonate solution with the concentration of 0.5-1mol/L can be dripped on the prepared three-dimensional compact rolling cobaltosic oxide material; then carrying out high-temperature reaction in a tubular furnace filled with oxygen. Transmission electron microscope characterization shows that the high-temperature lithiation in the step synthesizes the lithium cobaltate polycrystalline material of the rhombohedral crystal system.
Thus, the preparation of the target three-dimensional compact roll-stacked lithium cobaltate thin film material is completed.
In the embodiment shown in fig. 2 to 3, a three-dimensional densely-rolled lithium cobaltate thin film material is disclosed, which is a three-dimensional structure formed by densely rolling a two-dimensional thin film with a uniform thickness in a standing state, and the overall height (viewed in 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 micron, and the distance between the adjacent two-dimensional films is about 0.1 micron to 100 microns, preferably 0.3 micron to 10 microns. The surface of the two-dimensional film can be smooth, can also have a periodic ridge line structure, or can have both a periodic ridge line structure and a periodic pore structure. The three-dimensional compact roll-stacked lithium cobaltate thin film material can be prepared by the method, but is not limited to the method.
In the preparation process of the three-dimensional compact roll-stacked lithium cobaltate thin film material, the two-dimensional thin film can be provided with a smooth surface, a surface with periodic ridge lines or a surface with both periodic ridge lines and periodic pore structures by controlling the type of a driving power supply signal for electrochemical growth, such as a constant signal or a periodic signal, and the width, height and period of the ridge lines and the size and period of pores can be adjusted by the frequency and amplitude of the power supply signal.
The invention is further illustrated by the following examples and figures.
Example 1: a three-dimensional dense roll-stacked thin film material of lithium cobaltate.
0.02mol/L cobalt chloride solution is prepared to be used as electrolyte, a silicon chip substrate is selected as a lower substrate, a cobalt sheet is adopted as an electrode, and the lower substrate is placed on the silicon chip substrate. The electrolyte is dropped on a silicon chip substrate, a cover glass is covered on the silicon chip substrate to serve as an upper substrate, and the silicon chip substrate and the cover glass are placed in the middle of a heat preservation chamber together. And (5) cooling by using a constant-temperature water bath to condense the electrolyte. Thereafter, a periodic electrical 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 three-dimensional compact rolled film material sample of metal cobalt obtained under the condition, the macroscopic size of the sample reaches millimeter magnitude, the thickness of a two-dimensional film is uniform, and the sample presents a regular three-dimensional structure; the two-dimensional film had a smooth surface and a thickness of about 100 nm.
The three-dimensional compact rolling and folding film material of the metal cobalt is placed in the center of a tubular 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 cubic cobaltosic oxide polycrystalline material. Fig. 4a and 4b are comparison graphs of the morphology of the same sample before and after oxidation, and the lower graphs, fig. 4d and 4e, are transmission electron diffraction patterns of the sample under the same conditions, respectively, showing polycrystalline cobalt and cobaltosic oxide materials in a hexagonal system and a cubic system before and after oxidation of the sample, respectively.
Taking a cobaltosic oxide three-dimensional compact rolling sample as a precursor, dropwise adding a lithium carbonate solution on the prepared three-dimensional compact rolling cobaltosic oxide material to completely soak the sample, placing the sample in a tubular furnace, introducing oxygen, and carrying out high-temperature lithiation to fully react. Fig. 4b and 4c are comparative images of the same sample before and after lithiation, and fig. 4f is a transmission electron diffraction pattern of the sample after lithiation, and the result shows that this step of high temperature lithiation synthesizes a lithium cobaltate polycrystalline material of a rhombohedral crystal system.
Example 2: a three-dimensional dense roll-stacked thin film material of lithium cobaltate.
0.01mol/L cobalt sulfate solution is prepared to be used as electrolyte, an electrolytic cell is built by selecting a mica sheet substrate, and a cobalt wire with the diameter of 0.1mm is used as an electrode and is placed on the mica sheet substrate. The electrolyte is dropped on a mica sheet substrate, a cover glass is covered on the mica sheet substrate, and the mica sheet substrate and the cover glass are placed in the middle of a heat preservation chamber together. And (5) cooling by using a constant-temperature water bath to condense the electrolyte. Thereafter, a periodic electrical 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 is the three-dimensional dense rolling film material of metal cobalt obtained under the above conditions, wherein the two-dimensional film surface has a pore structure and also has a periodic ridge line structure, and the thickness is uniform.
The three-dimensional compact rolling and folding film material of the metal cobalt is placed in the center of a tubular furnace, oxygen is introduced, and high-temperature oxidation is carried out. In the same way as in example 1, cubic system cobaltosic oxide polycrystalline material was synthesized by high-temperature oxidation.
And putting the three-dimensional compact rolling sample of cobaltosic oxide into a tubular furnace as a precursor, dropwise adding a lithium carbonate solution on the prepared three-dimensional compact rolling cobaltosic oxide material, and introducing oxygen to carry out high-temperature lithiation. This step of high temperature lithiation synthesized a lithium cobaltate polycrystalline material of rhombohedral crystal system as in example 1.
Finally, it should be noted that while the above describes exemplifying embodiments of the invention with reference to the accompanying drawings, the invention is not limited to the embodiments and applications described above, which are merely illustrative and instructive, and not restrictive. Those skilled in the art, having the benefit of this disclosure, may effect numerous modifications thereto without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. A three-dimensional compact rolled lithium cobaltate thin film material is characterized by being constructed into a three-dimensional structure, wherein the three-dimensional structure is formed by standing and compactly rolling two-dimensional lithium cobaltate thin films with uniform thickness; the two-dimensional lithium cobaltate thin film is configured to have a smooth surface, or a surface having a periodic ridge line structure, or a surface having a periodic ridge line and a periodic pore structure.
2. The three-dimensional dense roll-stacked lithium cobaltate thin film material according to claim 1, wherein the thickness of the two-dimensional lithium cobaltate thin film is 50nm to 1 um; the distance between the adjacent two-dimensional lithium cobaltate films is 0.1-100 um, preferably 0.3-10 um.
3. The three-dimensional dense roll-stacked lithium cobaltate thin film material according to claim 1, wherein the height of the three-dimensional stereo structure is 10 um-5 mm, preferably 50 um-2 mm.
4. A lithium ion battery, characterized in that the positive electrode is made of the three-dimensional compact rolled lithium cobaltate thin film material of any one of claims 1 to 3.
5. A method for preparing the three-dimensional dense roll-stacked lithium cobaltate thin film material according to any one of claims 1 to 3, which is characterized by comprising the following steps:
s1, providing an electrolytic cell; adjusting the temperature of electrolyte in the electrolytic cell to be near the freezing point to condense the electrolyte, then driving the electrochemical deposition between a cathode and an anode in the electrolytic cell through a power supply signal, carrying out electrochemical growth on a deposit from a cathode to an anode in the electrolyte, and preparing a three-dimensional compact rolling film material of metal cobalt after the growth is finished; the electrolyte in the electrolytic cell is cobalt salt, and the anode material of the electrode is metal cobalt; the power supply signal is a constant signal or a periodic signal;
s2, performing high-temperature oxidation by using the three-dimensional compact rolling and folding film material of the metal cobalt as a precursor to prepare a three-dimensional compact rolling and folding cobaltosic oxide film material;
and S3, carrying out high-temperature lithiation by taking the cobaltosic oxide thin film material as a precursor to prepare the three-dimensional compact roll-stacked lithium cobaltate thin film material.
6. The method according to claim 5, wherein when the power supply signal is a constant signal, the two-dimensional lithium cobaltate thin film is configured to have a smooth surface; when the power supply signal is a periodic signal, the two-dimensional lithium cobaltate thin film is constructed to be a surface with a periodic ridge line structure or a surface with 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 the height of the ridge line structure are adjusted through the frequency and the amplitude of the periodic signal.
7. The method of claim 5, wherein the cobalt salt is cobalt naphthenate, cobalt stearate, cobalt neodecanoate, CoF2、CoSO4、CoCl2、Co(NO3)2Or a mixture of at least two thereof; the concentration of the cobalt salt is 0.01-1 mol/L.
8. The method of claim 5, wherein the electrolytic cell is a sandwich structure comprising an upper substrate, a lower substrate, and an electrode and an electrolyte disposed between the upper substrate and the lower substrate.
9. The method of claim 5, 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 adjusted by adjusting the temperature of the constant-temperature water bath system.
10. The method according to claim 5, wherein the step S2 specifically includes: placing a three-dimensional compact rolling sample of metal cobalt in a tubular furnace in an oxygen atmosphere for high-temperature oxidation, and synthesizing a cubic cobaltosic oxide polycrystalline material after the high-temperature oxidation;
the step S3 specifically includes: dropwise adding a lithium carbonate solution on the three-dimensional compact rolling cobaltosic oxide film material; then carrying out high-temperature lithiation in a tube furnace in an oxygen atmosphere to synthesize a lithium cobaltate polycrystalline material of a rhombohedral crystal system; the concentration of the lithium carbonate solution is 0.5-1 mol/L.
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Citations (9)
| 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 |
| US20190058212A1 (en) * | 2017-08-17 | 2019-02-21 | Seiko Epson Corporation | Composite body, lithium battery, and electronic apparatus |
| US20190348669A1 (en) * | 2018-04-12 | 2019-11-14 | Massachusetts Institute Of Technology | Electrodes comprising composite mixtures and related devices and methods |
Patent Citations (9)
| 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 |
| US20190058212A1 (en) * | 2017-08-17 | 2019-02-21 | Seiko Epson Corporation | Composite body, lithium battery, and electronic apparatus |
| US20190348669A1 (en) * | 2018-04-12 | 2019-11-14 | Massachusetts Institute Of Technology | Electrodes comprising composite mixtures and related devices and methods |
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