CN108365255B - Lithium battery cell, lithium battery and preparation method of lithium battery cell - Google Patents

Lithium battery cell, lithium battery and preparation method of lithium battery cell Download PDF

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CN108365255B
CN108365255B CN201711370999.9A CN201711370999A CN108365255B CN 108365255 B CN108365255 B CN 108365255B CN 201711370999 A CN201711370999 A CN 201711370999A CN 108365255 B CN108365255 B CN 108365255B
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lithium
current collector
lithium battery
layer
positive electrode
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CN108365255A (en
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张晓琨
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Chengdu Dachao Technology Co ltd
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
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    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0423—Physical vapour deposition
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0423—Physical vapour deposition
    • H01M4/0426—Sputtering
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract

The invention relates to the field of lithium batteries, in particular to a lithium battery cell, a lithium battery and a preparation method thereof, wherein a current collector comprises two oppositely arranged positive pole faces and negative pole faces, a lithium-containing oxide columnar crystal positive pole layer is formed on the positive pole faces to serve as a positive pole structure of the lithium battery cell, a lithium silicon carbon composite negative pole layer is formed on the negative pole layer, and lithium-containing oxide columnar crystals with high voltage and high capacity characteristics are used as positive pole materials to obtain the lithium battery cell and the lithium battery with high capacity density. The positive and negative electrodes which are respectively divided into two different lithium battery cell units are arranged on the two surfaces of the current collector to form the positive and negative common electrode current collector, so that the lamination preparation of a plurality of lithium battery cell units can be realized, the preparation of a large-capacity lithium battery can be realized, and the current collector can be directly used as an external electrode of the lithium battery, so that the packaging structure of the lithium battery is simplified.

Description

Lithium battery cell, lithium battery and preparation method of lithium battery cell
Technical Field
The invention relates to the field of lithium batteries, in particular to a lithium battery cell, a lithium battery and a preparation method thereof.
Background
The lithium battery has the advantages of good safety, good cycle performance and the like, becomes an important development direction of the secondary battery, and has larger market application potential compared with other sodium ion batteries due to the fact that the atomic radius of the metal lithium element is small and the lowest electrochemical potential is achieved.
Three key factors affecting the performance of lithium batteries are safety, specific capacity and high rate characteristics. In the prior art, the most mature graphite negative electrode is adopted as a lithium battery core material system, the theoretical capacity of the lithium battery core material system is only 270mAh/g, and the positive electrode material is materials with lower specific capacities such as lithium iron phosphate, ternary materials, lithium cobaltate and the like, so that the battery energy density can only reach 250-300Wh/kg. The combination of the positive electrode and the negative electrode used at present cannot realize large-voltage charging, so that the current situation of low multiplying power of the current lithium battery is caused. Accordingly, there is a need to provide a solution for low power of lithium batteries.
Disclosure of Invention
In order to solve the problem of poor multiplying power characteristics of the existing lithium battery, the invention provides a lithium battery cell, a lithium battery and a preparation method thereof.
The invention provides a technical scheme for solving the technical problems as follows: the utility model provides a lithium battery cell, its includes current collector, columnar crystal positive pole layer, lithium silicon carbon composite negative pole layer, diaphragm and liquid electrolyte, the current collector includes first current collector and the second current collector of relative setting, first current collector orientation has a positive pole face towards the second current collector orientation, the second current collector orientation has a negative pole face, columnar crystal positive pole layer forms on the positive pole face, lithium silicon carbon composite negative pole layer forms on the negative pole face, the diaphragm complex in between columnar crystal positive pole layer and the lithium silicon carbon composite negative pole layer, the infiltration has liquid electrolyte in the diaphragm.
Preferably, the first current collector further comprises a negative electrode surface opposite to the positive electrode surface, a lithium silicon carbon composite negative electrode layer of another lithium battery cell is formed on the negative electrode surface, the second current collector further comprises a positive electrode surface opposite to the negative electrode surface, and a columnar crystal positive electrode layer of another lithium battery cell is formed on the positive electrode surface.
Preferably, a protective layer is further arranged on the surface of the lithium silicon carbon composite anode layer, which is close to the diaphragm, for preventing electrolyte from corroding the lithium silicon carbon composite anode layer, a filling layer is further arranged on the columnar crystal anode layer, for filling gaps in the columnar crystal anode layer between the current collector and the diaphragm, and the protective layer and the filling layer are any one or more of oxide or sulfide solid electrolytes.
Preferably, it is characterized in that: one end of the diaphragm is compounded on the surface of the protective layer, which is far away from the lithium silicon carbon composite negative electrode layer, in a hot-pressing manner, and the other end of the diaphragm is compounded on one end of the columnar crystal positive electrode layer, which is far away from the current collector.
Preferably, one end of the columnar crystal positive electrode layer far away from the current collector is in direct contact with the diaphragm, and the thickness of the columnar crystal positive electrode layer is 10nm-100 μm; the columnar crystal positive electrode layer comprises a lithium-containing oxide positive electrode material, wherein the lithium-containing oxide positive electrode material comprises one or more of a lithium cobaltate positive electrode, a lithium nickelate positive electrode, a lithium manganate positive electrode, a lithium iron phosphate positive electrode and a derivative positive electrode thereof, a nickel cobalt manganese ternary positive electrode and a derivative positive electrode thereof, and a nickel cobalt aluminum ternary positive electrode and a derivative positive electrode thereof.
Preferably, the diaphragm mainly comprises any one of a PP film, a PE film, a PP-PE composite film, a PP-ceramic film or a PE ceramic film, and the thickness of the diaphragm is 15-40 mu m.
Preferably, the liquid electrolyte mainly comprises a lithium salt electrolyte and an organic solvent, wherein the lithium salt electrolyte mainly comprises any one or more of inorganic lithium salt LiAlM, liM, liXFn (M is a halogen element, X is B, as, P, sb and the like, and n is 4 or 6) and organic lithium salt LiCF 3SO3、LiN(SO2CF3)2 and derivatives thereof; the organic solvent comprises essentially either PC, EC, DEC, DMC, EC 2 DMC or PC 2 DMC.
Preferably, the lithium silicon carbon composite anode layer comprises a silicon-lithium alloy deposited on the anode surface of the current collector and carbon nano-particles composited in the silicon-lithium alloy, and the thickness of the lithium silicon carbon composite anode layer is 10nm-100 μm.
The invention provides a technical scheme for solving the technical problems as follows: a lithium battery comprises the lithium battery cells, and a plurality of lithium battery cells can be connected in parallel or connected in series by sharing a current collector.
The invention provides a technical scheme for solving the technical problems as follows: a preparation method of a lithium battery comprises the following steps:
s11, providing a first current collector, forming a columnar crystal positive electrode layer containing lithium oxide on one surface of the first current collector, and filling a filling layer in a gap of the positive electrode layer containing lithium oxide;
S12, providing a second current collector, forming a lithium silicon carbon composite anode layer on one surface of the second current collector, and forming a protective layer on the surface of the lithium silicon carbon composite anode layer, which is far away from the second current collector;
s13, providing a prefabricated diaphragm layer, and compounding the diaphragm layer on the surface of the columnar crystal positive electrode layer far away from the first current collector and the surface of the protective layer far away from the lithium silicon carbon composite negative electrode layer in a hot pressing manner;
S14, forming a lithium silicon carbon composite anode layer of another lithium battery cell unit on the opposite side of the first current collector, where the columnar crystal anode layer is arranged, and forming a protective layer on the surface of the lithium silicon carbon composite anode layer, which is far away from the first current collector;
S15, forming a columnar crystal positive electrode layer of another lithium battery cell unit on the opposite side of the second current collector, provided with the lithium silicon carbon composite negative electrode layer, and filling a filling layer in a gap of the columnar crystal positive electrode layer;
S16, providing a third current collector, forming a columnar crystal positive electrode layer containing lithium oxide on one surface of the third current collector, providing a fourth current collector, and forming a lithium silicon carbon composite negative electrode layer on one surface of the fourth current collector;
s17, repeating the steps S13-S16 until the number of the lithium battery cells needed by the lithium battery is reached;
s18, providing a packaging structure and packaging the lithium battery;
and S19, providing a liquid electrolyte, and injecting the liquid electrolyte into the packaged lithium battery.
Compared with the prior art, the current collector structure, the lithium battery cell, the lithium battery and the preparation method thereof provided by the invention have the following beneficial effects:
The current collector provided by the invention comprises two opposite main surfaces, wherein a columnar crystal positive electrode layer containing lithium oxide is formed on one main surface to be used as a positive electrode structure of a lithium battery cell, and a lithium silicon carbon composite negative electrode layer is formed on the other main surface to be used as a negative electrode structure of the other lithium battery cell. The lithium-containing oxide is used as the columnar crystal positive electrode layer, and based on the characteristics of high voltage and high capacity, the volume energy density of the positive electrode layer material can be obviously increased, and meanwhile, the multiplying power characteristic of the lithium battery can be improved.
Further, by arranging the positive and negative electrodes on the two surfaces of the current collector to form the positive and negative common electrode current collector, the preparation of a plurality of lithium battery cell stacks can be realized, and the preparation of a large-capacity lithium battery can be realized.
The overall thickness of the lithium battery cell and the lithium battery can be reduced by utilizing the current collectors of the positive electrode and the negative electrode. Furthermore, the current collectors of the positive and negative common electrodes can be used for realizing series connection among a plurality of lithium battery cells. When lithium battery cells in the lithium battery are connected in series, the current collector can be directly used as an external electrode of the lithium battery, the packaging structure of the lithium battery can be simplified, and hundreds of lithium battery cells can be connected in series at the same time, so that the lithium battery with voltage reaching kilovolts and larger capacity can be obtained.
In the invention, the lithium battery cell comprises a second current collector and a lithium silicon carbon composite anode layer formed on the surface of the columnar crystal anode layer facing the second current collector, wherein the thickness ratio between the lithium oxide-containing columnar crystal anode layer and the lithium silicon carbon composite anode layer is inversely proportional to the specific capacity density between materials composing the lithium oxide-containing columnar crystal anode layer and the lithium silicon carbon composite anode layer. Based on different thickness settings of the columnar crystal positive electrode layer and the lithium silicon carbon composite negative electrode layer material, the utilization rate of the columnar crystal positive electrode layer can be further improved, and therefore the performance of the lithium battery can be improved.
In the invention, the columnar crystal structure of the lithium-containing oxide is adopted, so that smooth diffusion and migration channels can be provided for lithium ions in the charge and discharge process, and the maximum utilization of the anode material is realized by matching with the high-performance anode, and the efficiency of lithium intercalation and deintercalation is improved. The lithium battery cell and the lithium battery can further adopt a lithium silicon carbon composite anode layer which is formed on one surface of the anode current collector facing the lithium silicon carbon anode structure, and the thickness of the lithium silicon carbon composite anode layer is 10nm-100 mu m. The columnar crystal anode material containing lithium oxide is matched with the lithium silicon carbon anode material, so that the utilization rate of the anode layer can be improved, and the preparation of the high-voltage high-capacity lithium battery can be further obtained.
The lithium battery cell and the lithium battery provided by the invention further comprise a carbon-based material layer, wherein the carbon-based material layer can be formed between the anode layer and the second current collector. The arrangement of the carbon-based material layer can enhance conductivity, so that the stability and safety of the lithium battery cell and the lithium battery are improved.
According to the lithium battery cell and the lithium battery, the filling layer is arranged in the gaps of the columnar crystals, so that the transmission of lithium ions in the columnar crystal positive electrode layer is further enhanced.
Further, a protective layer is arranged between the lithium silicon carbon composite anode layer and the diaphragm, and the protective layer and the filling layer are respectively oxide or sulfide solid electrolyte, so that the transmission of lithium ions is effectively ensured, meanwhile, the diaphragm and the liquid electrolyte are effectively isolated by the protective layer, the lithium silicon carbon composite anode layer is effectively prevented from being corroded by the liquid electrolyte, and the service life of the lithium battery is prolonged.
According to the preparation method of the lithium battery, the columnar crystal positive electrode layer can be formed on any main surface of the current collector; the current collector comprises at least two metals, and by using the method, the lithium battery can be prepared in a large area, so that the large-scale preparation of the low cost can be realized.
Drawings
Fig. 1 is a schematic layer structure of a current collector structure according to a first embodiment of the present invention.
Fig. 2A is a schematic layer structure of a lithium battery cell according to a second embodiment of the present invention.
Fig. 2B is a schematic layer structure of a lithium battery cell according to a third embodiment of the present invention.
Fig. 3 is a schematic layer structure of a lithium battery cell according to another embodiment of the present invention.
Fig. 4 is a schematic layer structure of a lithium battery cell according to a fourth embodiment of the invention.
Fig. 5 is a schematic structural view of a lithium battery according to a fifth embodiment of the present invention.
Fig. 6 is a schematic structural view of a lithium battery according to a sixth embodiment of the present invention.
Fig. 7 is a schematic structural view of a lithium battery according to a seventh embodiment of the present invention.
Fig. 8 is a flow chart of a method for preparing a lithium battery according to an eighth embodiment of the invention.
Detailed Description
For the purpose of making the technical solution and advantages of the present invention more apparent, the present invention will be further described in detail below with reference to the accompanying drawings and examples of implementation. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Referring to fig. 1, in a first embodiment of the present invention, a current collector structure 100 is provided, where the current collector structure 100 includes a current collector 101, and the current collector 101 includes two opposite main surfaces 109, where one main surface 109 is formed with a positive electrode layer 102 to serve as a positive electrode structure of a lithium battery cell, and the other main surface 109 is formed with a negative electrode layer 103 to serve as a negative electrode structure of another lithium battery cell.
In the present invention, the positive electrode layer 102 includes an oxide positive electrode material, and a lithium cobalt oxide positive electrode, a lithium nickel oxide positive electrode, a lithium manganese oxide positive electrode, a lithium iron phosphate positive electrode and its derivative positive electrode, a nickel cobalt manganese ternary positive electrode and its derivative positive electrode, and the like, a nickel cobalt aluminum ternary positive electrode and its derivative positive electrode, and the like.
The negative electrode layer 103 may include, but is not limited to: a metal lithium, a composite anode of metal lithium and silicon, carbon or one of the metal lithium and the silicon, the silicon anode, the silicon-carbon composite anode, the graphite anode, the lithium titanate anode, the carbon-based anode and the like. In the present invention, a lithium silicon carbon material is preferable as the negative electrode material.
In this and all the following embodiments of the present invention, the following are defined for the current collector materials: the current collector may comprise a simple substance metal or a metal alloy obtained by one or a combination of several other metals such as Cu, al, ni, ag, au, cr, ta or Ti.
Referring to fig. 2A, a second embodiment of the present invention provides a lithium battery cell 10, which includes a current collector, a columnar crystalline positive electrode layer 111, a lithium-silicon-carbon composite negative electrode layer 112, a separator 16 and a liquid electrolyte 17. The current collector comprises a first current collector 11 and a second current collector 12 which are oppositely arranged, wherein the surface of the first current collector 11 facing the second current collector 12 is a positive electrode surface 110, and the surface of the second current collector 12 facing the first current collector 11 is a negative electrode surface 120. A columnar crystal positive electrode layer 111 is formed on the positive electrode surface 110 to serve as a positive electrode structure of the lithium battery cell 10, and a lithium silicon carbon composite negative electrode layer 112 is formed on the negative electrode surface 120 to serve as a negative electrode structure of the lithium battery cell 10. The separator 16 is thermally pressed and compounded between the columnar crystal positive electrode layer 111 and the lithium silicon carbon composite negative electrode layer 112, and the liquid electrolyte 17 is positioned between the positive electrode layer 111 and the negative electrode layer 112 and is immersed in the separator 16.
Referring to fig. 2B, a third embodiment of the present invention provides a lithium battery cell 10, which includes a first current collector 11 and a second current collector 12 disposed opposite to each other, wherein the first current collector 11 includes a set of opposite positive electrode surfaces 1101 and negative electrode surfaces 1102, a columnar crystal positive electrode layer 111 is formed on the positive electrode surfaces 1101 to serve as a positive electrode structure of the lithium battery cell 10, and a lithium silicon carbon composite negative electrode layer 112 is formed on the negative electrode surfaces 1102 to serve as a negative electrode structure of another lithium battery cell 10. The second current collector 12 also includes a set of opposite positive electrode surface 1201 and negative electrode surface 1202, wherein the negative electrode surface 1201 is formed with a lithium-silicon-carbon composite negative electrode layer 121 to serve as a negative electrode structure of the lithium battery cell 10, and the positive electrode surface 1202 of the second current collector 12 is formed with a positive electrode layer 122 to serve as a positive electrode structure of another lithium battery cell 10. The diaphragm 16 is thermally pressed and compounded between the columnar crystal positive electrode layer 111 and the lithium silicon carbon composite negative electrode layer 121, and the liquid electrolyte 17 is positioned between the columnar crystal positive electrode layer 111 and the lithium silicon carbon composite negative electrode layer 121 and is immersed in the diaphragm 16.
Referring to fig. 3, in some embodiments of the present invention, the columnar crystals 1111 are regularly arranged to form a columnar crystal positive electrode layer 111, so as to provide a stable transmission channel for lithium ions, and can reversibly insert lithium, and the columnar crystal positive electrode layer 111 can have a higher capacity density.
In particular, columnar crystals 1111 disposed adjacently tend to be densely arranged without gaps therebetween. When the gap between the columnar crystals 1111 tends to zero, the greater the number of the columnar crystals 1111 that can be set in the range of the same area, the further the energy density of the positive electrode structure obtained therefrom can be improved; when there is a gap between the columnar crystals 1111, the columnar crystal positive electrode layer 111 further includes a filling layer 1112, and the filling layer 1112 is used for filling the gap between the columnar crystals 1111. In the present embodiment, the positive electrode layer 111 adopts columnar crystals 1111 having a larger surface area, and further, by providing a filler layer 1112 in the columnar crystal positive electrode layer 11, more reaction interfaces are provided between the liquid electrolyte 17 and the columnar crystal positive electrode layer 111 in the formed lithium battery 10.
Further, the lithium silicon carbon composite anode layer can be prepared by forming a silicon-lithium alloy by adopting PVD (physical vapor deposition) technologies such as magnetron sputtering, electron beam evaporation, pulse laser deposition and atomic layer deposition, and then further compounding carbon nano particles in the silicon-lithium alloy by adopting a hot pressing technology.
Specifically, before hot pressing, the carbon nano particles can be dissolved in lithium salt solution to form coating slurry, then the coating slurry is coated on the surface of the lithium-silicon composite anode, and then the lithium-silicon composite anode is heated and pressurized by a high-temperature corrosion-resistant substrate, so that the slurry enters the lithium-silicon alloy in a hot pressing way, and the slurry solution volatilizes and disperses under the action of high temperature, so that the required lithium-silicon-carbon composite anode layer is obtained.
With continued reference to fig. 3, a protective layer 1211 is formed on the surface of the lithium-silicon-carbon composite negative electrode layer 121 adjacent to the separator 16, the surface of the separator 16 adjacent to the lithium-silicon-carbon composite negative electrode layer 121 is thermally pressed and compounded on the protective layer 1211, and the other opposite surface of the separator 16 is thermally pressed and compounded on the end of the columnar crystal positive electrode layer 111 away from the current collector 11. It will be appreciated that the lithium silicon carbon composite anode layer 121 of the lithium battery cell 10 of the present invention is not in contact with the separator 16, and the end of the columnar crystal cathode layer 111 away from the current collector 11 is directly in contact with the separator 16. Further, the protective layer 1211 and the filler layer 18 are any one or more of sulfide or oxide solid state electrolytes including one or more of perovskite type solid electrolyte, NASICON type solid electrolyte, garnet type solid state electrolyte, liGePS type sulfide solid state electrolyte, liSiPS type sulfide solid state electrolyte, or LiSnPS type sulfide solid state electrolyte; the oxide solid electrolyte comprises any one or more of a SiO 2、B2O3、P2O5 mixture and a network modified oxide Li 2 O solid electrolyte.
The diaphragm 16 comprises any one of a PP film, a PE film, a PP-PE composite film, a PP-ceramic film or a PE ceramic film, and the thickness of the diaphragm 16 is 15-45 mu m; the thickness of the membrane 16 may also be 16-40 μm; in particular, the thickness of the membrane 16 may also be 16 μm, 18 μm, 20 μm, 25 μm or 40 μm.
The liquid electrolyte 17 mainly comprises a lithium salt electrolyte and an organic solvent, wherein the lithium salt electrolyte mainly comprises any one or more of inorganic lithium salt LiAlM, liM, liXFn (M is a halogen element, X is B, as, P, sb and the like, and n is 4 or 6) and organic lithium salt LiCF 3SO3、LiN(SO2CF3)2 and derivatives thereof; the organic solvent comprises essentially either PC, EC, DEC, DMC, EC 2 DMC or PC 2 DMC.
In the present invention, the thicknesses of the first and second current collectors 11 and 12 are 10nm to 100 μm, and in particular, the thicknesses of the first and second current collectors 11 and 12 may be 10nm, 15nm, 20nm, 24nm, 56nm, 143nm, 350nm, 567nm, 778nm, 983nm, 1 μm, 19 μm, 31 μm, 45 μm, 50 μm, 61 μm, 76 μm, 89 μm or 100 μm.
In the present invention, in order to make the lithium battery cell 10 have more excellent performance and improve the utilization rate of the columnar crystal positive electrode layer 111, in some embodiments of the present invention, the thickness relationship between the columnar crystal positive electrode layer 111 and the lithium silicon carbon composite negative electrode layer 121 may be further defined. Specifically, the thickness relationship between the columnar crystal positive electrode layer 111 and the lithium silicon carbon composite negative electrode layer 121 is related to the materials selected for the two.
The relation can be expressed as the following formula (1):
ρpositive×vpositive=ρnegative×vnegative
Ρpositive×spositive×dpositive=ρnegative×snegative×dnegative (1)
As can be seen from the above formula, in the same lithium battery cell, the areas S of the positive electrode layer 111 and the lithium silicon carbon composite negative electrode layer 121 are equal to the areas S minus, and therefore, the thicknesses of the columnar crystal positive electrode layer 111 and the lithium silicon carbon composite negative electrode layer 121 are inversely proportional to the energy densities of the materials thereof.
In the present invention, the ratio of the thickness of the above-mentioned crystalline positive electrode layer to the lithium silicon carbon composite negative electrode layer may be 100 to 0.01.
When the columnar crystal positive electrode layer 111 includes positive electrode columnar crystals of lithium iron phosphate and derivatives thereof, the thickness ratio between the columnar crystal positive electrode layer 111 and the lithium silicon carbon composite negative electrode layer 121 is about 10:1. in some specific embodiments of the present invention, the columnar crystalline positive electrode layer 111 has a thickness of 10nm to 100 μm; specifically, the thickness of the columnar crystalline positive electrode layer 111 may be further: may be 10nm, 15nm, 20nm, 24nm, 56nm, 143nm, 350nm, 567nm, 778nm, 983nm, 1 μm, 19 μm, 31 μm, 45 μm, 50 μm, 61 μm, 76 μm, 89 μm or 100 μm.
In some specific embodiments of the present invention, the lithium silicon carbon composite anode layer 121 has a thickness of 10nm to 100 μm; the thickness of the lithium silicon carbon composite anode layer 121 may be further: 10nm, 15nm, 20nm, 24nm, 56nm, 143nm, 350nm, 567nm, 778nm, 983nm, 1 μm, 19 μm, 31 μm, 45 μm, 50 μm, 61 μm, 76 μm, 89 μm or 100 μm.
In some specific implementations of the present embodiment, as shown in fig. 3, the columnar crystalline positive electrode layer 111 may include an oxide having a columnar crystal structure, and the columnar crystalline positive electrode layer 111 includes at least one layer of columnar crystals 1111.
The positive electrode layer 111 includes columnar crystals 1111 containing lithium oxide, and the columnar crystals are regularly arranged. Therefore, a smooth diffusion and migration path for lithium ions in the charge and discharge process can be provided to facilitate lithium intercalation and deintercalation, thereby improving the rate characteristics of the lithium battery and enabling the positive electrode layer 111 to have a higher capacity density.
Specifically, when the gap between the columnar crystals 1111 of the lithium-containing oxide tends to zero, the larger the number of the columnar crystals that can be provided in the range of the same area, the further the capacity density of the positive electrode structure obtained therefrom can be improved.
The dimensions of columnar crystals 1111 described herein and below refer to the dimensions along the thickness direction of the positive electrode structure. The columnar crystals 1111 have a size of 1nm to 100 μm. In some embodiments of the present invention, the columnar crystals 1111 have a size of 1nm、3nm、5nm、7nm、10nm、17nm、23nm、26nm、46nm、57nm、101nm、143nm、350nm、567nm、778nm、983nm、1μm、19μm、31μm、45μm、50μm、61μm、76μm、89μm or 100 μm.
In some embodiments of the present invention, the columnar crystalline positive electrode layer 111 and the lithium-silicon-carbon composite negative electrode layer 121 may be formed by deposition on one surface of the first current collector 11 using PVD techniques such as magnetron sputtering, electron beam evaporation, pulsed laser deposition, and atomic layer deposition.
In this embodiment, the lithium-silicon-carbon composite anode layer 121 may be formed by depositing a silicon-lithium alloy by PVD techniques such as magnetron sputtering, electron beam evaporation, pulsed laser deposition, atomic layer deposition, etc., and further by compounding carbon nanoparticles into the silicon-lithium alloy by a hot pressing technique.
Specifically, before hot pressing, the carbon nano particles can be dissolved in lithium salt solution to form coating slurry, then the coating slurry is coated on the surface of the lithium-silicon composite anode, and then the lithium-silicon composite anode is heated and pressurized by a high-temperature corrosion-resistant substrate, so that the slurry enters the lithium-silicon alloy in a hot pressing way, and the slurry solution volatilizes and disperses under the action of high temperature, so that the required lithium-silicon-carbon composite anode layer is obtained.
With continued reference to fig. 3, in the first embodiment of the present embodiment, in the lithium battery cell 10, the thickness of the protection layer 1211 is 1-3000nm. Specifically, the thickness of the protective layer 1211 is 1nm、3nm、5nm、7nm、10nm、17nm、23nm、26nm、46nm、57nm、101nm、143nm、350nm、567nm、778nm、983nm、1000nm、1500nm、2100nm、2189nm or 3000nm.
According to the lithium-silicon-carbon composite negative electrode layer 121 and the diaphragm 16, the protective layer 1211 is arranged between the lithium-silicon-carbon composite negative electrode layer 121 and the diaphragm 16, so that lithium ions are effectively conducted, meanwhile, the lithium-silicon-carbon composite negative electrode layer 121 and the diaphragm 16 are isolated, the liquid electrolyte 17 is effectively prevented from corroding the lithium-silicon-carbon composite negative electrode layer 121, and the service life of the lithium battery cell 10 is prolonged.
With continued reference to fig. 4, a fourth embodiment of the present invention provides a lithium battery cell 20, which is different from the lithium battery cells in the second embodiment and the third embodiment in that: the lithium battery cell 20 further includes a carbon-based material layer 29. The carbon-based material layer 29 is specifically a graphite thin layer, a carbon nanotube, a graphene thin film layer, a fullerene thin film layer, or the like, and is only used as an example herein, and is not limiting of the present invention.
The carbon-based material layer 29 serves to improve electric field distribution at the surface of the negative electrode, enhance conductivity, facilitate intercalation or deintercalation of the lithium negative electrode, and inhibit formation of lithium dendrites at the lithium negative electrode. As shown in fig. 5, in further embodiments of the present invention, the carbon-based material layer 29 may be disposed between the negative electrode layer 221 and the second current collector 22.
In some embodiments of the present invention, the carbon-based material layer 29 is formed on the surface of the negative electrode layer 221 facing the second current collector 22 through a hot pressing process, so that the carbon-based material layer 29 can realize gradient carbon material distribution with a certain depth inside the negative electrode layer 221, and form cladding and supporting to a certain extent on the negative electrode layer 221, so as to enhance the strength of the negative electrode layer 221 and avoid collapse of the negative electrode layer 221.
In some specific embodiments of the present invention, the carbon-based material layer 29 may further be formed on the surface of the negative electrode layer 221 facing the second current collector 22 by coating a carbon-based material layer 29 having a desired thickness.
Referring to fig. 5, a lithium battery 30 is provided in a fifth embodiment of the present invention, the lithium battery 30 may include two first lithium battery cell units 301 and second lithium battery cell units 302 that are sequentially stacked, a positive and negative common electrode current collector 31 is shared between the lithium battery cell units 301 and the lithium battery cell units 302, the positive and negative common electrode current collector 31 includes two opposite positive electrode surfaces 3101 and negative electrode surfaces 3102, and a columnar crystal positive electrode layer 311 is formed on the positive electrode surface 3101 to serve as a positive electrode structure of the first lithium battery cell 301; a lithium silicon carbon composite anode layer 312 is formed on the anode surface 3102 to serve as an anode structure of the second lithium battery cell unit 302.
Also included in the first lithium battery cell 301 is a negative current collector 32, and the second lithium battery cell 302 includes a positive current collector 35. A lithium silicon carbon composite anode layer 321 is formed on the side of the anode current collector 32 facing the columnar crystal anode layer 311, and a lithium oxide containing columnar crystal anode layer 351 is disposed on the surface of the anode current collector 35 facing the positive and negative common electrode current collector 31. The relevant limitations of the lithium-silicon-carbon composite anode layer 321 and the columnar crystalline cathode layer 351 are as described in the above second embodiment and the third embodiment, and are not repeated here. A diaphragm 36 and a liquid electrolyte 37 are further arranged between the columnar crystal positive electrode layer 311 and the lithium silicon carbon composite negative electrode layer 321, and the liquid electrolyte 37 is soaked in the diaphragm 36; meanwhile, a separator 36 and a liquid electrolyte 37 are also arranged between the lithium silicon carbon composite anode layer 312 and the columnar crystal cathode layer 351, and the liquid electrolyte 37 is soaked in the separator 36.
Further, the lithium battery 30 further includes a filling layer 3112 and a filling layer 3511 filled in the gaps between the columnar crystal positive electrode layer 311 and the positive electrode columnar crystal layer 351, and a protective layer 3211 and a protective layer 3112 are disposed on the surfaces of the lithium silicon carbon composite negative electrode layer 312 and the lithium silicon carbon composite negative electrode layer 321 facing the separator 36.
In another embodiment of the present invention, the first lithium battery cell 301 and the second lithium battery cell 302 may be any one of the lithium battery cell 10 or the lithium battery cell 20 of the second embodiment or the third embodiment, and the specific layer structure thereof may be adjusted according to the actual battery performance requirement, which is only used as an example and not as a limitation of the present invention.
In other embodiments of the present invention, two lithium battery cells in a lithium battery may be connected in parallel, and the connection manner is the same as that of the existing parallel-connected battery, which is not described herein.
In other embodiments of the present invention, when the lithium battery may further include more than two lithium battery cells, at least some of the lithium battery cells are formed into a whole by continuous lamination, and a positive and negative common electrode current collector is shared between the two lithium battery cells; and the current collectors of the lithium battery cells arranged at the two ends only play a role of positive current collectors or negative current collectors.
Referring specifically to fig. 6, a sixth embodiment of the present invention provides a lithium battery 40, where the lithium battery 40 includes a plurality of lithium battery cells 10 arranged in a continuous stack. The lithium battery 40 can be manufactured by stacking layers, wherein the specific stacking number of the lithium battery cell units 10 is preferably 300-400.
The lithium battery cell unit 10 includes a first current collector 41, a columnar crystal positive electrode layer 44, a filling layer 442, a diaphragm 46, a liquid electrolyte 47, a protective layer 451, a lithium-silicon-carbon composite negative electrode layer 45 and a second current collector 42 which are stacked. The adjacently disposed lithium battery cells 10 are stacked together by sharing a second current collector 42.
As shown in fig. 6, the second current collector 42 is shared at the overlapping portion of two lithium battery cell units 10 disposed adjacently, that is, the second current collector 42 is a positive and negative common electrode current collector. As shown in the figure, a columnar crystal positive electrode layer 44 and a lithium silicon carbon composite negative electrode layer 45 are provided on both sides of the second current collector 42, respectively. The plurality of lithium battery cells 10 may be connected in series. When the lithium battery cell units in the lithium battery are connected in series, the current collectors at the two ends can be directly used as the outer electrodes of the lithium battery, so that the packaging structure of the lithium battery is simplified.
Referring to fig. 7, in a seventh embodiment of the present invention, a lithium battery 50 is provided, in this embodiment, the lithium battery 50 includes 5 lithium battery cells, which are a first lithium battery cell 501, a second lithium battery cell 502, a third lithium battery cell 503, a fourth lithium battery cell 504 and a fifth lithium battery cell 505 that are sequentially stacked. The plurality of lithium battery cells may include: first current collector 51, columnar crystal positive electrode layer 54, filling layer 542, separator 56, liquid electrolyte 57, protective layer 551, lithium silicon carbon composite negative electrode layer 55, and second current collector 52.
The first lithium battery cell unit 501 and the second lithium battery cell unit 502 share the second current collector 52, and two opposite surfaces of the second current collector 52 are provided with the lithium-silicon-carbon composite anode layer 55, so that the first lithium battery cell 501 and the second lithium battery cell 502 can be connected in parallel.
The second current collector 52 is also shared between the second lithium battery cell 502 and the third lithium battery cell 503, and the positive electrode layer 54 and the negative electrode layer 55 are respectively disposed on two opposite main surfaces of the second current collector 52, so that the second lithium battery cell 502 and the third lithium battery cell 503 may be connected in series.
Further, the second current collector 532 of the third lithium battery cell 503 and the first current collector 541 of the fourth lithium battery cell 504 are stacked, and the first current collector 532 and the second current collector 541 are respectively denoted as positive current collectors or negative current collectors of the third lithium battery cell 503 and the fourth lithium battery cell 504. It can be seen that the third lithium battery cell 503 and the fourth lithium battery cell 504 may form a parallel connection relationship through an external circuit.
In this embodiment, the relative positions of the columnar crystal positive electrode layer 54 and the lithium-silicon-carbon composite negative electrode layer 55, the first current collector 51, and the second current collector 52 are adjustable.
The lithium battery 50 shown in fig. 7 is only an example, and in the actual lithium battery 50, the specific connection manner may be adjusted according to the performance requirements of the actual lithium battery, which is not limited by the present invention.
With continued reference to fig. 8, an eighth embodiment of the present invention provides a method S10 for preparing a lithium battery, wherein one embodiment includes the following steps:
step S11, providing a first current collector, and forming a columnar crystal positive electrode layer on one surface of the first current collector;
step S12, filling a filling layer in the gap of the columnar crystal positive electrode layer;
step S13, providing a second current collector, and forming a lithium silicon carbon composite anode layer on one surface of the second current collector;
step S14, forming a protective layer on the surface of the lithium silicon carbon composite anode layer far away from the second current collector;
Step S15, providing a prefabricated diaphragm layer, and compounding the diaphragm layer on the surface of the columnar crystal positive electrode layer far away from the first current collector and the surface of the protective layer far away from the lithium silicon carbon composite negative electrode layer in a hot pressing manner;
And S16, packaging the structure, providing liquid electrolyte, and injecting the liquid electrolyte into the packaged structure to obtain a single lithium battery.
To this end, the above steps S11 to S16 complete the preparation of the single lithium battery.
In other specific implementations of this embodiment, the step S15 may further include the following steps:
step S16a, forming a lithium silicon carbon composite anode layer of another lithium battery cell unit on the opposite surface of the first current collector provided with the columnar crystal anode layer, and forming a protective layer on the surface of the lithium silicon carbon composite anode layer far away from the first current collector;
Step S17a, forming a columnar crystal positive electrode layer of another lithium battery cell unit on the opposite side of the second current collector provided with the lithium silicon carbon composite negative electrode layer, and filling a filling layer in a gap of the columnar crystal positive electrode layer;
step S18a, providing a third current collector, forming a columnar crystal positive electrode layer on one surface of the third current collector, providing a fourth current collector, and forming a lithium silicon carbon composite negative electrode layer on one surface of the fourth current collector;
and step S19a, repeating the steps S15-S18a until the lithium battery reaches the required number of the lithium battery cell units.
In step S20a, a packaging structure is provided to package the lithium battery, a liquid electrolyte is provided, and the liquid electrolyte is injected into the packaged lithium battery.
Specifically, regarding the thickness and the material selection of the first current collector, the second current collector, the columnar crystal positive electrode layer, the lithium-silicon-carbon composite negative electrode layer, and the protective layer in the above steps are described in the above second embodiment and the third embodiment, and are not repeated here.
In particular, in the above-mentioned method S10 for manufacturing a lithium battery, before forming the columnar crystal positive electrode layer or the lithium-silicon-carbon composite negative electrode layer on the first current collector and/or the second current collector, it is necessary to planarize the upper surface of the first current collector and/or the second current collector to ensure the surface of the current collector to be flat. Wherein, the planarization treatment can adopt a chemical mechanical polishing process, and an abrasive and a polishing machine are used for carrying out local polishing and grinding.
In some specific embodiments of the present invention, in the step S11, the columnar crystal positive electrode layer formed on the current collector and containing lithium oxide may be prepared by using a magnetron sputtering grazing incidence method:
(1) Setting an included angle between the direction vertical to the substrate and the direction vertical to the target material in a substrate such as a magnetron sputtering cavity to be larger than 45 degrees, and keeping the substrate at room temperature by water cooling;
(2) Vacuumizing to 10 < -5 > Pa, introducing argon, and adjusting the working pressure of the cavity to 2Pa to start depositing the lithium iron phosphate anode material;
(3) And simultaneously, the substrate rotates, and columnar crystals of the 2-micrometer lithium-containing oxide are formed after 50 minutes of deposition.
The above-described method for preparing the columnar crystal positive electrode layer for lithium-containing oxide is merely an example, and is not a limitation of the present invention.
Compared with the prior art, the current collector structure, the lithium battery cell, the lithium battery and the preparation method thereof provided by the invention have the following beneficial effects:
The current collector provided by the invention comprises two opposite main surfaces, wherein a columnar crystal positive electrode layer containing lithium oxide is formed on one main surface to be used as a positive electrode structure of a lithium battery cell, and a lithium silicon carbon composite negative electrode layer is formed on the other main surface to be used as a negative electrode structure of the other lithium battery cell. The lithium-containing oxide is used as the columnar crystal positive electrode layer, and based on the characteristics of high voltage and high capacity, the volume energy density of the positive electrode layer material can be obviously increased, and meanwhile, the multiplying power characteristic of the lithium battery can be improved.
Further, by arranging the positive and negative electrodes on the two surfaces of the current collector to form the positive and negative common electrode current collector, the preparation of a plurality of lithium battery cell stacks can be realized, and the preparation of a large-capacity lithium battery can be realized.
The overall thickness of the lithium battery cell and the lithium battery can be reduced by utilizing the current collectors of the positive electrode and the negative electrode. Furthermore, the current collectors of the positive and negative common electrodes can be used for realizing series connection among a plurality of lithium battery cells. When lithium battery cells in the lithium battery are connected in series, the current collector can be directly used as an external electrode of the lithium battery, the packaging structure of the lithium battery can be simplified, and hundreds of lithium battery cells can be connected in series at the same time, so that the lithium battery with voltage reaching kilovolts and larger capacity can be obtained.
In the invention, the lithium battery cell comprises a second current collector and a lithium silicon carbon composite anode layer formed on the surface of the columnar crystal anode layer facing the second current collector, wherein the thickness ratio between the lithium oxide-containing columnar crystal anode layer and the lithium silicon carbon composite anode layer is inversely proportional to the specific capacity density between materials composing the lithium oxide-containing columnar crystal anode layer and the lithium silicon carbon composite anode layer. Based on different thickness settings of the columnar crystal positive electrode layer and the lithium silicon carbon composite negative electrode layer material, the utilization rate of the columnar crystal positive electrode layer can be further improved, and therefore the performance of the lithium battery can be improved.
In the invention, the columnar crystal structure of the lithium-containing oxide is adopted, so that smooth diffusion and migration channels can be provided for lithium ions in the charge and discharge process, and the maximum utilization of the anode material is realized by matching with the high-performance anode, and the efficiency of lithium intercalation and deintercalation is improved. The lithium battery cell and the lithium battery can further adopt a lithium silicon carbon composite anode layer which is formed on one surface of the anode current collector facing the lithium silicon carbon anode structure, and the thickness of the lithium silicon carbon composite anode layer is 10nm-100 mu m. The columnar crystal anode material containing lithium oxide is matched with the lithium silicon carbon anode material, so that the utilization rate of the anode layer can be improved, and the preparation of the high-voltage high-capacity lithium battery can be further obtained.
The lithium battery cell and the lithium battery provided by the invention further comprise a carbon-based material layer, wherein the carbon-based material layer can be formed between the anode layer and the second current collector. The arrangement of the carbon-based material layer can enhance conductivity, so that the stability and safety of the lithium battery cell and the lithium battery are improved.
According to the lithium battery cell and the lithium battery, the filling layer is arranged in the gaps of the columnar crystals, so that the transmission of lithium ions in the columnar crystal positive electrode layer is further enhanced.
Further, a protective layer is arranged between the lithium silicon carbon composite anode layer and the diaphragm, and the protective layer and the filling layer are respectively oxide or sulfide solid electrolyte, so that the transmission of lithium ions is effectively ensured, meanwhile, the diaphragm and the liquid electrolyte are effectively isolated by the protective layer, the lithium silicon carbon composite anode layer is effectively prevented from being corroded by the liquid electrolyte, and the service life of the lithium battery is prolonged.
According to the preparation method of the lithium battery, the columnar crystal anode layer can be formed on any main surface of the current collector; the current collector comprises at least two metals, and by using the method, the lithium battery can be prepared in a large area, so that the large-scale preparation of the low cost can be realized.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the invention, but any modifications, equivalents, improvements, etc. within the principles of the present invention should be included in the scope of the present invention.

Claims (10)

1. The utility model provides a lithium cell electricity core which characterized in that: the lithium silicon carbon composite anode comprises a current collector, a columnar crystal anode layer, a lithium silicon carbon composite anode layer, a diaphragm and a liquid electrolyte, wherein the current collector comprises a first current collector and a second current collector which are oppositely arranged, the first current collector is provided with an anode face towards the second current collector, the second current collector is provided with a cathode face towards the first current collector, the columnar crystal anode layer is regularly arranged on the anode face, and the thickness of the columnar crystal anode layer is 10nm-100 mu m; the lithium silicon carbon composite anode layer is formed on the anode face, the diaphragm is compounded between the columnar crystal anode layer and the lithium silicon carbon composite anode layer, and liquid electrolyte is infiltrated in the diaphragm.
2. The lithium battery cell as set forth in claim 1, wherein: the first current collector also comprises a negative electrode surface which is opposite to the positive electrode surface, a lithium silicon carbon composite negative electrode layer of another lithium battery cell is formed on the negative electrode surface, the second current collector also comprises a positive electrode surface which is opposite to the negative electrode surface, and a columnar crystal positive electrode layer of another lithium battery cell is formed on the positive electrode surface.
3. The lithium battery cell of any one of claims 1 or 2, wherein: the lithium silicon carbon composite anode layer is characterized in that a protective layer is further arranged on the surface, close to the diaphragm, of the lithium silicon carbon composite anode layer and used for preventing electrolyte from corroding the lithium silicon carbon composite anode layer, a filling layer is further arranged on the columnar crystal anode layer and used for filling gaps in the columnar crystal anode layer between the current collector and the diaphragm, and the protective layer and the filling layer are any one or more of oxide or sulfide solid electrolytes.
4. A lithium battery cell as set forth in claim 3, wherein: and one end of the diaphragm is compounded on the surface, far away from the lithium-silicon-carbon composite negative electrode layer, of the protective layer, the current collector comprises a first current collector and a second current collector, and the other end of the diaphragm is compounded on one end, far away from the current collector, of the columnar crystal positive electrode layer in a hot-pressing manner.
5. The lithium battery cell as set forth in claim 4, wherein: the cylindrical crystal positive electrode layer is far away from one end of the current collector and is in direct contact with the diaphragm, the cylindrical crystal positive electrode layer comprises a lithium-containing oxide positive electrode material, and the lithium-containing oxide positive electrode material comprises one or more of a lithium cobaltate positive electrode, a lithium nickelate positive electrode, a lithium manganate positive electrode, a lithium iron phosphate positive electrode and a derivative positive electrode thereof, a nickel cobalt manganese ternary positive electrode and a derivative positive electrode thereof, and a nickel cobalt aluminum ternary positive electrode and a derivative positive electrode thereof.
6. The lithium battery cell as set forth in claim 4, wherein: the diaphragm comprises any one of a PP film, a PE film, a PP-PE composite film, a PP-ceramic film or a PE ceramic film, and the thickness of the diaphragm is 15-40 mu m.
7. The lithium battery cell as set forth in claim 6, wherein: the liquid electrolyte comprises a lithium salt electrolyte and an organic solvent, wherein the lithium salt electrolyte comprises inorganic lithium LiAlM, liM, liXFn (M is a halogen element, X is B, as, P, sb, and n is 4 or 6) and any one or more of organic lithium salt LiCF 3SO3、LiN(SO2CF3)2 and derivatives thereof; the organic solvent comprises either PC, EC, DEC, DMC, EC 2 DMC or PC 2 DMC.
8. The lithium battery cell as set forth in claim 4, wherein: the lithium silicon carbon composite anode layer comprises a silicon-lithium alloy deposited on the anode surface of the current collector and carbon nano-particles compounded in the silicon-lithium alloy, wherein the thickness of the lithium silicon carbon composite anode layer is 10nm-100 mu m.
9. A lithium battery, characterized in that: the lithium battery cell of any one of claims 4-8, wherein a plurality of lithium battery cells are connected in parallel or a common current collector is connected in series.
10. A method for preparing a lithium battery, comprising:
s11, providing a first current collector, forming a columnar crystal positive electrode layer on one surface of the first current collector, and filling a filling layer in a gap of the positive electrode layer containing lithium oxide;
S12, providing a second current collector, forming a lithium silicon carbon composite anode layer on one surface of the second current collector, and forming a protective layer on the surface of the lithium silicon carbon composite anode layer, which is far away from the second current collector;
s13, providing a prefabricated diaphragm layer, and compounding the diaphragm layer on the surface of the columnar crystal positive electrode layer far away from the first current collector and the surface of the protective layer far away from the lithium silicon carbon composite negative electrode layer in a hot pressing manner;
S14, forming a lithium silicon carbon composite anode layer of another lithium battery cell unit on the opposite surface of the first current collector, which is provided with the columnar crystal anode layer, and forming a protective layer on the surface of the lithium silicon carbon composite anode layer, which is far away from the first current collector;
S15, forming a columnar crystal positive electrode layer of another lithium battery cell unit on the opposite side of the second current collector, which is provided with the lithium silicon carbon composite negative electrode layer, and filling a filling layer in a gap of the columnar crystal positive electrode layer;
s16, providing a third current collector, forming a columnar crystal positive electrode layer on one surface of the third current collector, providing a fourth current collector, and forming a lithium silicon carbon composite negative electrode layer on one surface of the fourth current collector;
s17, repeating the steps S13-S16 until the number of the lithium battery cells needed by the lithium battery is reached;
s18, providing a packaging structure and packaging the lithium battery;
and S19, providing a liquid electrolyte, and injecting the liquid electrolyte into the packaged lithium battery.
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