CN113161157B - Silicon-based composite anode active material, silicon-based composite anode, and preparation method and application thereof - Google Patents

Silicon-based composite anode active material, silicon-based composite anode, and preparation method and application thereof Download PDF

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CN113161157B
CN113161157B CN202110441457.6A CN202110441457A CN113161157B CN 113161157 B CN113161157 B CN 113161157B CN 202110441457 A CN202110441457 A CN 202110441457A CN 113161157 B CN113161157 B CN 113161157B
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silicon
based composite
negative electrode
active material
lithium
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CN113161157A (en
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孙现众
马衍伟
张熊
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Institute of Electrical Engineering of CAS
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Institute of Electrical Engineering of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative 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
    • 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
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention relates to the technical field of electrode materials, and provides a silicon-based composite anode active material, a silicon-based composite anode, and a preparation method and application thereof. The silicon-based composite negative active material provided by the invention comprises 30-82% of a silicon-based material, 0-10% of a one-dimensional carbon material and 18-60% of conductive carbon black. The invention realizes the synergistic effect on one-dimensional, two-dimensional and three-dimensional scales by compounding the silicon-based material, the one-dimensional carbon material and the conductive carbon black, avoids the particle pulverization and the failure of the silicon material caused by the volume change during the lithium insertion and the lithium removal, and can improve the electronic conductivity of the silicon-based composite cathode material. The silicon-based composite cathode prepared by the cathode active material has good power performance, high specific capacity and good cycle performance, is applied to a lithium ion energy storage device, and has excellent electrochemical performance.

Description

Silicon-based composite anode active material, silicon-based composite anode, and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrode materials, in particular to a silicon-based composite anode active material, a silicon-based composite anode, and a preparation method and application thereof.
Background
The lithium ion capacitor is a novel energy storage device, has higher power density and longer cycle life compared with a lithium ion battery, and can improve the energy density by 3-6 times compared with a double electric layer super capacitor. The positive electrode of the lithium ion capacitor usually adopts an activated carbon material with a high specific surface area, and the negative electrode adopts graphite, hard carbon, soft carbon, lithium titanate material and the like. However, the conventional negative electrode materials have low specific capacity, for example, the theoretical specific capacity of graphite is only 372mAh/g, and the voltage of a lithium titanate discharge platform is relatively high, so that the requirement of a high-energy-density lithium ion capacitor cannot be met.
The silicon-based material has the advantages of very high specific capacity (the theoretical specific capacity of silicon is 4200 mAh/g), slightly higher than a discharge platform of a carbon material, abundant energy storage and the like, so that the silicon-based material is concerned by researchers. However, the material is accompanied with severe volume expansion and shrinkage in the process of lithium intercalation and deintercalation, so that the silicon material is crushed, pulverized and desquamated, the capacity is rapidly attenuated, and the cycle performance is poor; in addition, silicon is a semiconductor material and has poor conductivity. The common solution is to adopt a silicon and carbon material composite mode, for example, patents with publication numbers of CN 106252572A, CN 106450434A, CN 105990602A, CN 106602028, and CN 107248451 all adopt silicon-carbon composite materials as the negative electrode materials of high-energy density lithium ion batteries. However, when the silicon-carbon composite material is used as the anode material, the obtained energy storage device has low specific capacity (generally 400-600 mAh/g), poor power performance and poor cycle performance.
Disclosure of Invention
In view of this, the invention provides a silicon-based composite anode active material, a silicon-based composite anode, and a preparation method and application thereof. The silicon-based composite negative electrode active material provided by the invention has high electronic conductivity, is not easy to break, pulverize and fall off in the lithium intercalation and deintercalation process, is applied to the negative electrode of a lithium ion energy storage device, and has good power performance, high specific capacity and good cycle performance.
In order to achieve the above object, the present invention provides the following technical solutions:
a silicon-based composite anode active material comprises the following components in percentage by mass: 30-82% of silicon-based material, 0-10% of one-dimensional carbon material and 18-60% of conductive carbon black; the silicon-based material comprises one or more of silica, nano silicon particles and silicon nanowires.
Preferably, the particle size of the nano silicon particles is less than or equal to 250nm, and the diameter of the silicon nanowires is less than or equal to 200nm.
Preferably, the one-dimensional carbon material comprises one or more of single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon whiskers and vapor grown carbon fibers.
The invention also provides a silicon-based composite negative electrode, which comprises a current collector and a coating arranged on the surface of the current collector; the coating comprises the following components in percentage by mass: 5-30% of binder and 70-95% of silicon-based composite active material as claimed in any one of claims 1-3.
Preferably, the current collector includes a copper foil, a copper foam, or a conductive carbon cloth.
Preferably, the binder comprises one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose, styrene butadiene rubber and LA type binders.
The invention also provides a preparation method of the silicon-based composite cathode, which comprises the following steps:
mixing the raw materials of the binder and the silicon-based composite negative active material, and coating the obtained mixed slurry on the surface of a current collector;
or, sequentially mixing and extruding the raw materials of the binder and the silicon-based composite negative active material to form a film, and laminating the obtained film on the surface of the current collector.
Preferably, the mixing method comprises ball milling mixing, stirring mixing, homogenizing mixing or extrusion mixing; the coating method comprises spray coating, transfer coating or extrusion coating.
The invention also provides the application of the silicon-based composite cathode in the scheme or the silicon-based composite cathode prepared by the preparation method in the scheme in a lithium ion energy storage device.
Preferably, the lithium ion energy storage device is a lithium ion capacitor, a lithium ion battery or a lithium ion battery capacitor.
The invention provides a silicon-based composite anode active material which comprises the following components in percentage by mass: 30-82% of silicon-based material, 0-10% of one-dimensional carbon material and 18-60% of conductive carbon black; the silicon-based material comprises silicon monoxide one or more of nano silicon particles and silicon nanowires. In the invention, the conductive carbon black can adsorb electrolyte, accelerate ion transmission and provide more expansion space, so that the silicon material is not pulverized when expanded and contracted; the one-dimensional carbon material has good tensile strength, can play a toughening effect, ensures that the silicon material cannot generate particle pulverization and failure when the volume of the silicon material expands and contracts after lithium insertion and lithium removal, and improves the cycle performance of the electrode; and the silicon material is wrapped between the two carbon materials, so that the electronic conductivity is remarkably increased, and the capacity retention rate of the negative electrode under the high-current density (the capacity retention rate under the high-current density refers to the ratio of the capacity under the high-current density to the rated capacity, and the higher the capacity retention rate under the high-current density is, the better the power performance of the electrode is), is also correspondingly and greatly increased, so that the power performance of the electrode is remarkably improved. The invention realizes the synergistic effect on one-dimensional, two-dimensional and three-dimensional scales by compounding the silicon-based material, the one-dimensional carbon material and the conductive carbon black, and obtains the cathode active material with good cycle performance, high specific capacity and good power performance.
The invention also provides a silicon-based composite negative electrode, which comprises a current collector and a coating arranged on the surface of the current collector; the components of the coating comprise a binder and the silicon-based composite active material in the scheme. The negative electrode prepared by the silicon-based composite material has good power performance, high specific capacity and good cycle performance.
The invention also provides a preparation method of the composite negative electrode, which adopts a mixed coating mode to prepare a coating on the surface of the current collector, or firstly mixes and extrudes raw materials to form a film, and then laminates the film on the surface of the current collector. The preparation method adopts a mechanical mixing and coating mode, and compared with the method for preparing the cathode material by chemical synthesis in the traditional method, the cost of the method can be reduced by more than 30 percent.
The invention also provides application of the silicon-based composite cathode in the scheme in a lithium ion energy storage device. The silicon-based composite cathode provided by the invention can be applied to various lithium ion energy storage devices, and the obtained devices have excellent electrochemical performance. The embodiment result shows that the capacity retention rate of the lithium ion capacitor assembled by the silicon-based composite negative electrode can reach 98% at 20 ℃.
Drawings
Fig. 1 shows the results of the capacity retention rate test of composite anodes with different conductive carbon black contents in example 1.
Detailed Description
The invention provides a silicon-based composite anode active material which comprises the following components in percentage by mass: 30-82% of silicon-based material, 0-10% of one-dimensional carbon material and 18-60% of conductive carbon black.
Unless otherwise specified, each raw material used in the present invention is commercially available.
The silicon-based composite negative electrode active material provided by the invention comprises 30-82% of silicon-based material, preferably 40-80%, and further preferably 45-75%. In the invention, the silicon-based material comprises one or more of silicon monoxide, nano silicon particles and silicon nanowires, the particle size of the nano silicon particles is preferably less than or equal to 250nm, more preferably less than or equal to 200nm, further preferably 20-150 nm, and the diameter of the silicon nanowires is preferably less than or equal to 200nm, more preferably less than or equal to 150nm, further preferably 30-150 nm; the particle size of the silica is not particularly required in the present invention, and silica having a particle size known to those skilled in the art may be used.
The silicon-based composite negative electrode active material provided by the invention comprises 0-10% of one-dimensional carbon material, preferably 1-8%, and more preferably 3-6%. In the present invention, the one-dimensional carbon material preferably includes one or more of single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon whiskers and Vapor Grown Carbon Fibers (VGCF); the present invention does not require the size of the one-dimensional carbon material, and the one-dimensional carbon material having a size known to those skilled in the art may be used.
The silicon-based composite negative active material provided by the invention comprises 18-60% of conductive carbon black, preferably 20-55%, and more preferably 25-50%. In the invention, the conductive carbon BLACK is a commercial product, and the specific model is preferably Super P Li, super C45, super C65, BP2000, VXC200 or DENKA BLACK; the particle size of the primary particles of the conductive carbon black is less than 100nm, and the primary particles form secondary particles with chain structures under the action of electrostatic attraction and van der Waals force. In the invention, the conductive carbon black can adsorb electrolyte, accelerate ion transmission and provide more expansion space, so that the silicon material is not pulverized when expanded and contracted; the inventor finds that in the silicon-based composite negative active material, the conductive carbon black is changed in quality after increasing to a certain amount, and the capacity retention rate of the negative electrode under high rate is obviously improved at the moment, but after the amount of the conductive carbon black is increased to a certain amount, the capacity retention rate is not improved any more, the liquid absorption amount is greatly increased, and the unit volume capacity is rapidly reduced; based on the rule, the content of the conductive carbon black is controlled to be 18-60%.
The invention also provides a silicon-based composite negative electrode, which comprises a current collector and a coating arranged on the surface of the current collector; the coating comprises the following components in percentage by mass: 5-30% of binder and 70-95% of silicon-based composite active material.
In the present invention, the current collector preferably includes a copper foil, a copper foam, or a conductive carbon cloth; the copper foil can be a common copper foil without a pipe perforation or a perforated copper foil with a through hole; the aperture ratio of the perforated copper foil is preferably 25%; the perforation rate specifically refers to the ratio of the area of holes on the current collector to the area of the current collector; the perforated copper foil may allow lithium ions to pass through the electrode tabs and diffuse between the respective negative electrode tabs.
In the present invention, the composition of the coating comprises 5 to 30%, preferably 10 to 25% of a binder; the binder preferably comprises one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose, styrene butadiene rubber and LA type binders.
In the present invention, the components of the coating layer include 70 to 95%, preferably 75 to 90%, of the silicon-based composite active material described in the above scheme.
In the present invention, the thickness of the coating layer is preferably 5 to 100 μm.
The invention also provides a preparation method of the silicon-based composite cathode in the scheme, the invention provides two preparation methods which are respectively marked as a first method and a second method, and the following descriptions are respectively given:
the first method comprises the following steps:
mixing a binder and raw materials (comprising a silicon-based material, a one-dimensional carbon material and conductive carbon black) of a silicon-based composite negative active material, and coating the obtained mixed slurry on the surface of a current collector.
In the present invention, the mixing method preferably includes ball-milling mixing, stirring mixing, homogenizing mixing or extrusion mixing; the ball milling and mixing are preferably carried out using a planetary ball mill; the stirring and mixing are preferably carried out by using a planetary stirrer; the homogenizing and mixing is preferably carried out using a high-speed homogenizer; the extrusion mixing is preferably carried out by a screw machine; the invention has no special requirements on the specific operation conditions of the mixing mode, and the raw materials can be uniformly mixed. In the present invention, the method of coating preferably includes spray coating, transfer coating or extrusion coating; the present invention does not require special conditions for the above-described coating method, and those well known to those skilled in the art can be used.
In the invention, the second method comprises the following steps:
and sequentially mixing and extruding the binder and the raw materials (comprising the silicon-based material, the one-dimensional carbon material and the conductive carbon black) of the silicon-based composite negative active material to form a film, and laminating the obtained film on the surface of a current collector.
In the invention, the mixing temperature is preferably 60-120 ℃; the pressure of the press covering is preferably 1 to 20MPa.
According to the invention, the silicon-based composite cathode is prepared by adopting the scheme, only mechanical mixing and coating are involved in the process, chemical synthesis is not involved, and the preparation cost can be greatly reduced.
The invention also provides the application of the silicon-based composite cathode prepared by the preparation method in the scheme or the application of the silicon-based composite cathode prepared by the preparation method in a lithium ion energy storage device. In the invention, the lithium ion energy storage device is a lithium ion capacitor, a lithium ion battery or a lithium ion battery capacitor.
In the invention, when the lithium ion energy storage device is a lithium ion capacitor, the positive electrode active material of the lithium ion capacitor is a capacitor material, preferably a porous carbon material, and the porous carbon material is preferably at least one of activated carbon, carbon aerogel and graphene. In the lithium ion capacitor, a battery material and a capacitor material form an internal series structure, namely, the battery material and the capacitor material can be equivalently regarded as a battery element and a capacitor element which coexist in the same energy storage device to form an internal series structure.
In the invention, when the lithium ion energy storage device is a lithium ion battery, the positive active material of the lithium ion battery is preferably at least one of lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium cobalt oxide, lithium iron phosphate and a lithium-rich manganese-based positive material; the nickel cobalt lithium manganate is also called as a ternary cathode material and can be used in a chemical formula LiNi x Co y Mn z O 2 Expressed that it can be classified into LiNi and LiNi according to the composition of the transition metal element 1/3 Co 1/3 Mn 1/3 O 2 、LiNi 0.5 Co 0.2 Mn 0.3 O 2 、LiNi 0.6 Co 0.2 Mn 0.2 O 2 、LiNi 0.7 Co 0.2 Mn 0.1 O 2 、LiNi 0.8 Co 0.1 Mn 0.1 O 2 And may be represented by NCM111, NCM523, NCM622, NCM721, and NCM811, respectively.
In the invention, when the lithium ion energy storage device is a lithium ion battery capacitor, the positive active material of the lithium ion Chi Dianrong simultaneously comprises a battery material and a capacitor material; the battery material preferably comprises at least one of lithium cobalt manganese oxide, lithium nickel cobalt aluminate, lithium cobalt oxide, lithium iron phosphate and a lithium-rich manganese-based positive electrode material; the chemical formula of the nickel cobalt lithium manganate is consistent with the scheme, and the types of the selectable nickel cobalt lithium manganate are consistent with the scheme, so that the details are not repeated; the capacitor material is preferably a porous carbon material, and the porous carbon material is preferably at least one of activated carbon, carbon aerogel and graphene. In the lithium ion battery capacitor device, an internal parallel structure formed by a battery material and a capacitor material can be equivalently regarded as a battery element and a capacitor element which coexist in the same energy storage device to form an internal parallel structure.
In the present invention, the lithium ion energy storage device is preferably prepared according to the following method:
(1) Laminating or winding the negative electrode plate, the positive electrode plate and the diaphragm into a battery cell;
(2) Placing a battery core into a shell, wherein the tabs of the positive electrode and the negative electrode extend out of the shell, placing a metal lithium electrode into the shell, placing the metal lithium electrode opposite to the battery core and separating the metal lithium electrode from the battery core by using a diaphragm, and performing heat sealing on the shell after injecting electrolyte into the shell;
(3) And pre-embedding lithium into the negative electrode by an electrochemical method, then taking out the metal lithium electrode, pouring out the redundant electrolyte, and carrying out vacuum sealing to obtain the lithium ion energy storage device.
The negative electrode plate, the positive electrode plate and the diaphragm are laminated or wound into a battery cell. In the invention, the positive electrode plate preferably comprises a positive current collector and a positive coating coated on the surface of the positive current collector, and the selectable types of the positive current collectors are consistent with the scheme and are not described again; the components of the positive electrode coating preferably comprise a binder and a positive electrode active material, and the kind of the binder is consistent with the scheme, so that the description is omitted; the content of the binder and the positive active material in the positive coating is not particularly required, and the content is known by the person skilled in the art; the cathode electrode plate is the silicon-based composite cathode in the scheme; the negative electrode plate and the positive electrode plate are separated by a diaphragm; the present invention does not require a particular lamination or winding method, and may be practiced using methods well known to those skilled in the art. In a specific embodiment of the present invention, a plurality of negative electrode sheets or positive electrode sheets in a battery cell may be used, for example, when the battery cell is prepared by a lamination method, the structure of the battery cell is preferably: diaphragm/negative pole/diaphragm/positive pole/diaphragm …/negative pole/diaphragm; when the battery cell is prepared by adopting a winding method, the structure of the battery cell is preferably as follows: separator/negative electrode/separator/…/positive electrode/separator.
After the battery cell is obtained, the battery cell is placed in the shell, the tabs of the positive electrode and the negative electrode extend out of the shell, the metal lithium electrode is placed in the shell and is opposite to the battery cell and separated by the diaphragm, and the shell is subjected to heat sealing after electrolyte is injected into the shell. In the present invention, the electrolyte is preferably composed of a lithium-containing electrolyte salt, preferably at least one of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium bis-trifluoromethanesulfonylimide and lithium difluorosulfonylimide, and a solvent, preferably at least one of propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate and vinylene carbonate; the injection amount of the electrolyte is proper, so that the battery core is fully soaked.
In the present invention, the electrolyte salt, the solvent, the positive electrode active material, and the separator are commercially available.
After the shell is subjected to heat sealing, the lithium is pre-embedded into the negative electrode by an electrochemical method. The method for pre-lithium intercalation does not have special requirements, and a pre-lithium intercalation method well known to a person skilled in the art can be adopted. In a specific embodiment of the present invention, the method for pre-intercalating lithium preferably comprises the following 3: (1) Connecting a metal lithium electrode with a negative electrode of an external power supply, connecting a negative electrode plate with a positive electrode of the external power supply, and discharging at constant current to enable the total lithium intercalation amount to reach a design value, wherein the current of the constant current discharging is preferably 0.01-0.5 ℃; (2) Connecting a metal lithium electrode with the positive electrode of an external power supply, connecting a negative electrode plate with the negative electrode of the external power supply, and charging at constant current to enable the total lithium intercalation amount to reach a design value, wherein the current for constant current charging is preferably 0.01-0.5 ℃; (3) Connecting a metal lithium electrode with the positive electrode of an external power supply, connecting a negative electrode plate with the negative electrode of the external power supply, charging to 0V by constant current, then charging by constant voltage to enable the total lithium intercalation amount to reach the design value, wherein the current of constant current charging is preferably 0.01-0.5C, and the voltage of constant voltage charging (marked as U) 0 ) Preferably greater than 0 and equal to or less than 15V (0)<U 0 Less than or equal to 0.15V). In the present invention, the meaning of C represents the capacity of a battery when the battery is discharged to a terminal voltage at a rate of 5h according to the QB/T2502-2000 lithium ion secondary battery general specification, that is: 1C represents a current value of 1 time capacity, and 5C represents a current value of 5 times capacity.
In the invention, when the silicon-based materials in the silicon-based composite negative electrode active material are silicon monoxide and nano silicon materials, the ratio of the first cycle lithium removal capacity to the lithium insertion capacity (first cycle coulombic efficiency) of the negative electrode is not high and is generally lower than 80%, and the first cycle coulombic efficiency of the one-dimensional carbon material and the conductive carbon black is also lower than 80%, which can cause the consumption of first cycle lithium ions and the reduction of lithium storage capacity. Therefore, the anode needs to be subjected to a lithium pre-intercalation operation.
In the present invention, the amount of the pre-intercalated lithium is preferably not less than the first week irreversible capacity, preferably 20 to 90% of the lithium capacity during the first discharge of the negative electrode. The discharge process refers to a first lithium intercalation process after the negative electrode material and the lithium electrode are assembled into a half cell, and intercalation and irreversible capacity loss of lithium ions in the negative electrode occur in the process. For lithium ion batteries, the pre-lithium insertion amount only needs to compensate irreversible capacity loss in the first-cycle lithium insertion process, and for lithium ion capacitors and lithium ion Chi Dianrong, the anode potential is ensured to be in a proper working interval. Preferably, the lithium pre-intercalation amount of the lithium ion battery adopting the composite negative electrode is preferably 20-40% of the lithium capacity of the negative electrode in the first discharge process; the pre-embedded lithium amount of the lithium ion Chi Dianrong adopting the composite cathode is preferably 30-80% of the lithium capacity in the first discharge process of the cathode; the pre-lithium intercalation amount of the lithium ion capacitor adopting the composite cathode of the invention is preferably 60-90% of the lithium capacity in the first discharge process of the cathode.
After the pre-lithium embedding is finished, the metal lithium electrode is taken out, the redundant electrolyte is poured out, and vacuum sealing is carried out to obtain the lithium ion energy storage device.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Conductive carbon black and silica are used to form the silicon-based composite negative active material, wherein the mass fractions of the conductive carbon black are respectively controlled to be 5%, 10%, 18%, 20%, 30%, 40%, 60% and 70%, and the balance is silica.
The silicon-based composite negative active material is used for preparing a silicon-based negative electrode, wherein the current collector adopts a perforated copper foil, the aperture ratio of the perforated copper foil is 25%, and the coating comprises the following components: 15% of binder polyvinylidene fluoride and 85% of the silicon-based composite negative electrode active material.
The preparation method comprises the following steps: conductive carbon black, silicon oxide and polyvinylidene fluoride were ball-milled and mixed in a planetary ball mill, and then the resulting slurry was coated on the surface of a perforated copper foil, the coating thickness being 30 μm each.
The composite negative electrode and metallic lithium are combined into a half battery, and the capacity retention rate of the composite negative electrode under the current density of 0.75A/g is tested, and the result is shown in figure 1.
As can be seen from fig. 1, when the content of the conductive carbon black is less than 18%, the capacity retention rate of the composite negative electrode is low, when the content is between 18% and 60%, the capacity retention rate of the composite negative electrode is significantly increased, and when the addition amount of the conductive carbon black is continuously increased, the capacity retention rate of the negative electrode begins to decrease. The invention combines the rule to control the content of the conductive carbon black in the silicon-based composite negative active material to be 18-60%, and can ensure higher capacity retention rate.
Example 2
A silicon-based composite negative electrode comprises a current collector and a coating coated on the current collector, wherein the current collector is a perforated copper foil, and the aperture ratio of the perforated copper foil is 25%; the coating comprises the following components in percentage by mass: 15% of binder and 85% of silicon-based composite negative electrode active material, wherein the binder is sodium carboxymethylcellulose and styrene butadiene rubber, and the mass ratio of the sodium carboxymethylcellulose to the styrene butadiene rubber is 1:1; the silicon-based composite negative active material comprises 18% of conductive carbon black and 82% of silicon oxide by mass fraction.
The preparation method comprises the following steps: mixing conductive carbon black, silicon monoxide, sodium carboxymethylcellulose and styrene butadiene rubber, extruding to form a film to obtain a film layer with the thickness of 50 mu m, and laminating the film layer on the surface of the perforated copper foil to obtain the silicon-based composite negative electrode.
Assembling the silicon-based composite negative electrode and metal lithium into a half cell, and testing the electrochemical performance of the composite negative electrode; the test equipment used was a battery tester from Neware 4 series, shenzhen New Willer, and the same test equipment was used in the following examples. Through testing, the capacity retention rate of the composite cathode under the current density of 750mA/g is 40% (the capacity retention rate under the large current density refers to the ratio of the capacity under the large current density to the rated capacity, and the meanings of the capacity retention rate in the subsequent embodiments are the same); the specific capacity can reach 950mAh/g under the low current density of 50 mA/g; after 5000 weeks of cycle test under the condition of 5C, the capacity retention rate (which refers to the ratio of the capacity after the cycle test to the initial capacity, and the meaning of the capacity retention rate in the subsequent embodiment is the same) reaches 60%.
A lithium ion capacitor is formed by 11 silicon-based composite cathodes, 10 activated carbon anodes and diaphragms, and the method specifically comprises the following steps:
laminating a diaphragm/a negative electrode/a diaphragm/a positive electrode/a diaphragm/a negative electrode/a diaphragm in sequence to obtain a battery cell;
placing a battery core into a shell, wherein the tabs of a positive electrode and a negative electrode extend out of the shell, placing a metal lithium electrode into the shell, placing the metal lithium electrode opposite to the battery core and separating the metal lithium electrode from the battery core by using a diaphragm, and performing heat sealing on the shell after injecting a proper amount of electrolyte into the shell;
and connecting the metal lithium electrode with the negative electrode of an external power supply, connecting the negative electrode plate with the positive electrode of the external power supply, performing constant current discharge at 0.1C to ensure that the total lithium intercalation amount reaches 80% of the lithium capacity in the first discharge process of the negative electrode, then taking out the metal lithium electrode, and performing vacuum sealing to obtain the lithium ion capacitor. Wherein the electrolyte adopted is 1mol/L LiPF 6 The solvent of the solution is a mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate, and the volume ratio of the ethylene carbonate to the dimethyl carbonate to the diethyl carbonate is 1.
The electrochemical performance of the obtained lithium ion capacitor is tested, and the capacity retention rate of the lithium ion capacitor is 70% when the capacitance is 1100F and the capacitance is 20C.
Example 3
A silicon-based composite negative electrode comprises a current collector and a coating coated on the current collector, wherein the current collector is a perforated copper foil, and the aperture ratio of the perforated copper foil is 25%; the coating comprises the following components in percentage by mass: 20% of binder and 80% of silicon-based composite negative electrode active material, wherein the binder is sodium carboxymethylcellulose and styrene butadiene rubber, and the mass ratio of the sodium carboxymethylcellulose to the styrene butadiene rubber is 1:1; the silicon-based composite negative active material comprises, by mass, 37.5% of conductive carbon black and 62.5% of silica.
The preparation method comprises the following steps: mixing conductive carbon black, silicon monoxide, sodium carboxymethylcellulose and styrene butadiene rubber, extruding to form a film to obtain a film layer with the thickness of 20 mu m, and laminating the film layer on the surface of the perforated copper foil to obtain the silicon-based composite negative electrode.
And assembling the silicon-based composite negative electrode and metal lithium into a half cell, and testing the electrochemical performance of the composite negative electrode. Tests prove that the capacity retention rate of the composite cathode under the current density of 750mA/g is 80%, and the specific capacity under the small current density of 50mA/g can reach 1250mAh/g. After 5000 weeks of cyclic test under the condition of 5C, the capacity retention rate reaches 93 percent.
And (3) forming a lithium ion capacitor by 11 silicon-based composite negative electrodes, 10 active carbon positive electrodes and a diaphragm, wherein the assembling method is consistent with that of the embodiment 2, and the adopted electrolyte is consistent with that of the embodiment 2.
The electrochemical performance of the obtained lithium ion capacitor is tested, and the capacity retention rate of the lithium ion capacitor is 85% when the capacitance is 1100F and the capacitance is 20C.
Example 4
A silicon-based composite negative electrode comprises a current collector and a coating coated on the current collector, wherein the current collector is a perforated copper foil, and the aperture ratio of the perforated copper foil is 25%; the coating comprises the following components in percentage by mass: 20% of binder and 80% of silicon-based composite negative electrode active material, wherein the binder is sodium carboxymethylcellulose and styrene butadiene rubber, and the mass ratio of the sodium carboxymethylcellulose to the styrene butadiene rubber is 1:1; the silicon-based composite negative active material comprises, by mass, 32.5% of conductive carbon black, 5% of single-walled carbon nanotubes and 62.5% of silica.
The preparation method comprises the following steps: and (3) conducting carbon black, the single-walled carbon nanotube, the silicon monoxide, the sodium carboxymethylcellulose and the styrene butadiene rubber are subjected to ball milling and mixing in a planetary ball mill, and the obtained slurry is coated on the surface of the perforated copper foil to obtain the silicon-based composite negative electrode.
The silicon-based composite negative electrode and metal lithium are assembled into a half cell, and the electrochemical performance of the composite negative electrode is tested. Through tests, the capacity retention rate of the composite cathode under the current density of 750mA/g is 90%, and the specific capacity under the small current density of 50mA/g can reach 1320mAh/g. After 5000 weeks of cycle performance test under the condition of 5C, the capacity retention rate reaches 93 percent.
And (3) forming a lithium ion capacitor by 11 silicon-based composite negative electrodes, 10 active carbon positive electrodes and a diaphragm, wherein the assembly method is consistent with that of the embodiment 2, and the adopted electrolyte is consistent with that of the embodiment 2.
The electrochemical performance of the obtained lithium ion capacitor is tested, and the capacity retention rate of the lithium ion capacitor is 98% when the capacitance is 1100F and the capacitance is 20C.
Example 5
The preparation method of the silicon-based composite negative electrode is consistent with that of the embodiment 3;
assembling 11 composite negative electrodes and 10 positive electrodes into a lithium ion Chi Dianrong, wherein the adopted positive electrode comprises 15% of activated carbon and 85% of NCM523 in parts by mass, the adopted electrolyte is a 1mol/L solution of LiPF6, the solvent of the solution is a mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate, and the volume ratio of the ethylene carbonate to the dimethyl carbonate to the diethyl carbonate is 1; the assembly method is identical to example 2, and the pre-lithium intercalation amount is 60% of the lithium capacity of the negative electrode during the first discharge.
And (3) carrying out electrochemical performance test on the obtained lithium ion Chi Dianrong, wherein the capacity of the lithium ion battery capacitor is 1Ah through the test.
Example 6
The preparation method of the silicon-based composite negative electrode is consistent with that of the embodiment 3;
assembling 11 composite negative electrodes and 10 NCM523 positive electrodes into a lithium ion battery, wherein the adopted electrolyte is a 1mol/L LiPF6 solution, the solvent of the solution is a mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate, and the volume ratio of the ethylene carbonate to the dimethyl carbonate to the diethyl carbonate is 1; the assembly method is identical to example 2, and the pre-lithium intercalation amount is 30% of the lithium capacity of the negative electrode during the first discharge.
The electrochemical performance of the lithium ion Chi Dianrong is tested, and the capacity of the lithium ion battery is 6Ah through the test.
Example 7
Other conditions were the same as in example 2 except that only the silicon monoxide in the mixture was replaced with nano-sized silicon particles having a particle size of 50 nm.
And assembling the obtained silicon-based composite negative electrode and metal lithium into a half cell, and testing the electrochemical performance of the composite negative electrode. Through tests, the capacity retention rate of the composite cathode under the current density of 750mA/g is 75%, the specific capacity under the small current density of 50mA/g is 1450mAh/g, and after the composite cathode is circularly tested for 5000 weeks under the condition of 5C, the capacity retention rate reaches 89%.
The lithium ion capacitor was assembled according to the method of example 2, and the obtained lithium ion capacitor was subjected to electrochemical performance test, and it was tested that the capacity retention ratio was 92% in 1100F and 20C test.
Example 8
Other conditions were the same as in example 2 except that the silicon monoxide was replaced with silicon nanowires having a diameter of 150 nm.
And assembling the obtained silicon-based composite negative electrode and metal lithium into a half cell, and testing the electrochemical performance of the composite negative electrode. Through tests, the capacity retention rate of the composite cathode under the current density of 750mA/g is 80%, the specific capacity under the small current density of 50mA/g is 1150mAh/g, and after the composite cathode is subjected to a cyclic test for 5000 weeks under the condition of 5C, the capacity retention rate reaches 82%.
The lithium ion capacitor was assembled according to the method of example 2, and the obtained lithium ion capacitor was subjected to electrochemical performance test, and it was tested that the capacity of the lithium ion capacitor was 1100F, and the capacity retention rate was 95% in 20C test.
Example 9
Other conditions were the same as in example 4, in which only the single-walled carbon nanotubes were replaced with carbon whiskers.
And assembling the obtained silicon-based composite negative electrode and metal lithium into a half cell, and testing the electrochemical performance of the composite negative electrode. Through tests, the capacity retention rate of the composite cathode under the current density of 750mA/g is 88%, the specific capacity under the small current density of 50mA/g is 1180mAh/g, and after the composite cathode is subjected to a cyclic test for 5000 weeks under the condition of 5C, the capacity retention rate reaches 85%.
The lithium ion capacitor was assembled according to the method of example 4, and the obtained lithium ion capacitor was subjected to electrochemical performance test, and it was tested that the capacity of the lithium ion capacitor was 1100F, and the capacity retention rate was 91% in 20C test.
Example 10
Other conditions were the same as in example 4 except that only the single-walled carbon nanotubes were replaced with vapor grown carbon fibers.
And assembling the obtained silicon-based composite negative electrode and metal lithium into a half cell, and testing the electrochemical performance of the composite negative electrode. Through tests, the capacity retention rate of the composite cathode under the current density of 750mA/g is 92%, the specific capacity under the small current density of 50mA/g is 1420mAh/g, and after the composite cathode is subjected to a cyclic test for 5000 weeks under the condition of 5C, the capacity retention rate reaches 88%.
The lithium ion capacitor was assembled according to the method of example 4, and the obtained lithium ion capacitor was subjected to electrochemical performance test, and it was tested that the capacity retention ratio was 92% in 1100F and 20C test.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. A silicon-based composite negative electrode is characterized by comprising a current collector and a coating arranged on the surface of the current collector; the coating comprises the following components in percentage by mass: 5-30% of binder and 70-95% of silicon-based composite negative active material; the silicon-based composite anode active material comprises the following components in percentage by mass: 30-82% of silicon-based material, 0-10% of one-dimensional carbon material and 18-60% of conductive carbon black; the silicon-based material comprises one or more of silicon monoxide, nano silicon particles and silicon nanowires;
the preparation method of the silicon-based composite negative electrode comprises the following steps:
mixing the raw materials of the binder and the silicon-based composite negative active material, and coating the obtained mixed slurry on the surface of a current collector;
or, sequentially mixing and extruding the raw materials of the binder and the silicon-based composite negative active material to form a film, and laminating the obtained film on the surface of the current collector.
2. The silicon-based composite anode according to claim 1, wherein the particle size of the nano-silicon particles is less than or equal to 250nm, and the diameter of the silicon nanowires is less than or equal to 200nm.
3. The silicon-based composite anode according to claim 1, wherein the one-dimensional carbon material comprises one or more of single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon whiskers and vapor grown carbon fibers.
4. The silicon-based composite anode according to claim 1, wherein the current collector comprises copper foil, copper foam or conductive carbon cloth.
5. The silicon-based composite negative electrode as claimed in claim 1, wherein the binder comprises one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose, styrene butadiene rubber and LA type binder.
6. The method for preparing the silicon-based composite anode according to any one of claims 1 to 5, characterized by comprising the following steps:
mixing the raw materials of the binder and the silicon-based composite negative active material, and coating the obtained mixed slurry on the surface of a current collector;
or, sequentially mixing and extruding the raw materials of the binder and the silicon-based composite negative active material to form a film, and laminating the obtained film on the surface of the current collector.
7. The method of claim 6, wherein the mixing comprises ball-milling, stirring, homogenizing, or extrusion mixing; the coating method comprises spray coating, transfer coating or extrusion coating.
8. The silicon-based composite negative electrode according to any one of claims 1 to 5 or the silicon-based composite negative electrode prepared by the preparation method according to any one of claims 6 to 7 is applied to a lithium ion energy storage device.
9. The use according to claim 8, wherein the lithium ion energy storage device is a lithium ion capacitor, a lithium ion battery or a lithium ion battery capacitor.
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