CN114784281A - Composite lithium cathode of solid-state battery, preparation method of composite lithium cathode and solid-state battery - Google Patents

Composite lithium cathode of solid-state battery, preparation method of composite lithium cathode and solid-state battery Download PDF

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Publication number
CN114784281A
CN114784281A CN202210545349.8A CN202210545349A CN114784281A CN 114784281 A CN114784281 A CN 114784281A CN 202210545349 A CN202210545349 A CN 202210545349A CN 114784281 A CN114784281 A CN 114784281A
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lithium
composite
negative electrode
solid
state battery
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张强
温雪飞
闫崇
武鹏
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Shanxi Research Institute for Clean Energy of Tsinghua University
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Shanxi Research Institute for Clean Energy of Tsinghua University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/139—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
    • H01M4/36—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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a composite lithium cathode of a solid-state battery, a preparation method of the composite lithium cathode and the solid-state battery. The composite lithium negative electrode comprises metallic lithium and a plurality of interphase carbon microspheres which are arranged at intervals, wherein the metallic lithium is inserted into part of each interphase carbon microsphere to form a composite interface layer; the thickness of the composite lithium negative electrode is 100-1500 mu m. The mesocarbon microbeads of the composite lithium cathode of the solid-state battery have good chemical stability, high stacking density, easy graphitization and excellent electrical conductivity and thermal conductivity, the composite interface layer is beneficial to the insertion and the extraction of lithium ions from all directions of a sphere, and in the charging process, the lithium ions can be inserted into the mesocarbon material and can be stored in the micropores inside the mesocarbon microbeads, so that the problem of volume expansion of the battery can be effectively relieved, the growth of lithium dendrites is improved, and the cycle life of the battery is effectively prolonged.

Description

Composite lithium cathode of solid-state battery, preparation method of composite lithium cathode and solid-state battery
Technical Field
The invention belongs to the technical field of solid-state batteries, and particularly relates to a composite lithium cathode of a solid-state battery, a preparation method of the composite lithium cathode and the solid-state battery.
Background
With the rapid development of 3C consumer electronics, electric vehicles and power grid energy storage, higher requirements are put on the electrochemical performance, energy density and safety of batteries. In recent years, common batteries in the market, such as ternary batteries, LFP (lithium iron phosphate), lithium cobaltate, lithium manganate and the like, have been rapidly developed in various colleges and universities, research institutes and lithium battery companies, but the further application of the next generation portable power supply is limited by relatively low theoretical energy density and liquid electrolyte. Compared with the traditional graphite negative electrode (with the theoretical specific capacity of 372mAh/g), the metal lithium negative electrode has extremely high theoretical specific capacity (3860mAh/g) and extremely low reduction potential (with the reduction potential of-3.04V compared with a hydrogen standard electrode), so that the potential application of the metal lithium battery is promoted. Meanwhile, the liquid electrolyte is used, so that certain potential safety hazard exists, and the lithium metal cathode with higher energy density cannot be used due to the side reaction of the electrolyte and the metal lithium. However, the widespread use of metallic lithium cathodes has been challenged by various challenges such as uncontrolled lithium dendrites, the generation of powdered lithium, and the problem of large volume expansion of lithium during de-intercalation, which defects severely reduce the cycle life of the battery, preventing its use.
At present, the industry and academia have proposed many strategies to solve these problems of lithium negative electrode batteries, such as developing faster solid-state batteries, but when increasing energy density and increasing cycling capacity, this makes lithium dendrites easily break away from the electrode surface to form "dead lithium" which cannot be utilized, and at the same time, metallic lithium negative electrode batteries cause a huge volume expansion problem, resulting in failure of the electrolyte membrane (SEI) at the negative electrode side.
In recent years, a major breakthrough has been made in the development of 3D metallic lithium. The three-dimensional (3D) framework with lithium affinity points, such as N-doped graphene, graphene with rich edge structures, carbon nano-microspheres and the like, can provide places for deposition of metal lithium, and can effectively relieve the problem of volume expansion. Carbon materials are often used as framework materials due to their light weight and controlled surface chemistry. Therefore, finding a new method to realize the compounding of the metal lithium and the carbon material is very important in the practical process of the metal lithium battery.
Disclosure of Invention
The invention provides a composite lithium cathode of a solid-state battery, a preparation method thereof and the solid-state battery, and aims to solve the technical problems of poor stability and poor cycle performance of the solid-state battery.
The invention provides a composite lithium cathode of a solid-state battery, which comprises metallic lithium and a plurality of interphase carbon microspheres arranged at intervals, wherein part of each interphase carbon microsphere is inserted into the metallic lithium to form a composite interface layer; the thickness of the composite lithium negative electrode is 100-1500 mu m.
In some embodiments, the raw material of the mesocarbon microbeads includes any one or more of coal pitch, coal tar, petroleum residual asphalt, synthetic resin and synthetic asphalt.
In some embodiments, the lithium metal is lithium sheet with a thickness of 5-1100 μm, lithium ribbon or lithium metal powder with a particle size of 20-50 μm.
In some embodiments, the molar ratio of the lithium metal to the mesocarbon microbeads is 1:9 to 9: 1.
The second aspect of the present invention provides a method for preparing the lithium composite negative electrode of the solid-state battery, which comprises the following steps:
a) mixing, laminating or adhering the mesocarbon microbeads and the lithium metal to obtain a pretreatment structure;
b) heating, fusing or rolling the pretreatment structure to obtain a lithium cathode;
c) and placing the lithium negative electrode in an environment with a water value less than 1ppm and an oxygen value less than 1ppm for standing to form the composite lithium negative electrode with a composite interface layer.
In some embodiments, the rolling pressure in step b) is 0.1 to 100MPa, and the hot melting temperature is 25 to 200 ℃.
In some embodiments, the standing time of step c) is at least 1.5 hours, and the standing temperature is 25-200 ℃.
In some embodiments, the rolling in step b) is performed by any one or more of a roller, a punch or a tablet press.
In some embodiments, the theoretical specific capacity of the composite lithium negative electrode is 700-3600 mAh/g.
The third aspect of the invention provides a solid-state battery, which comprises the composite lithium negative electrode or the composite lithium negative electrode prepared by the preparation method.
The mesocarbon microbeads of the composite lithium cathode of the solid-state battery have good chemical stability, high stacking density, easy graphitization and excellent electrical conductivity and thermal conductivity, the composite interface layer is beneficial to the insertion and the extraction of lithium ions from all directions of a sphere, and in the charging process, the lithium ions can be inserted into the mesocarbon material and can be stored in the micropores inside the mesocarbon microbeads, so that the problem of volume expansion of the battery can be effectively relieved, the growth of lithium dendrites is improved, and the cycle life of the battery is effectively prolonged.
Drawings
Fig. 1 is a schematic structural diagram of a composite lithium negative electrode of a solid-state battery according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention clearer, the present invention is further described in detail with reference to the following embodiments. It should be understood that the embodiments described in this specification are only for the purpose of explaining the present invention and are not intended to limit the present invention.
For the sake of brevity, only a few numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual numerical value between the endpoints of a range is encompassed within that range. Thus, each point or individual value can form a range not explicitly recited as its own lower or upper limit in combination with any other point or individual value or in combination with other lower or upper limits.
In the description herein, it is noted that, unless otherwise specified, "a number" means one or more than one; "several" means two or more; the terms "above" and "below" are inclusive; the terms "upper," "lower," "inner," "outer," and the like, refer to an orientation or positional relationship that is based on the orientation or positional relationship shown in the drawings for ease of description and simplicity of description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and therefore should not be construed as limiting herein.
The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the present invention. The following description more particularly exemplifies illustrative embodiments. At various points throughout this application, guidance is provided through lists of examples, which examples can be used in various combinations. In each instance, the list is provided only as a representative group and should not be construed as exhaustive.
The first aspect of the embodiment of the present invention provides a composite lithium negative electrode of a solid-state battery, as shown in fig. 1, including metallic lithium 3 and a plurality of interphase carbon microspheres 1 arranged at intervals, where a portion of each interphase carbon microsphere 1 is inserted into the metallic lithium 3 to form a composite interface layer 2; the thickness of the composite lithium negative electrode is 100-1500 mu m.
Mesophase carbon microspheres 1(Mesocarbon Microbeads, MCMB for short) are optically anisotropic microspheres formed by a series of carbonization reactions such as thermal polycondensation-thermal cracking of polycyclic aromatic hydrocarbon compounds (such as coal-based pitch, petroleum-based pitch, naphthalene, etc.), which have a liquid phase morphology and a nematic liquid crystal structure and exist in a spherical morphology under the action of surface tension, and are called mesophase carbon microspheres 1. The mesocarbon microbeads 1 have good chemical stability, high bulk density, easy graphitization, good thermal stability and excellent electrical and thermal conductivity.
The mesocarbon microbeads 1 have a unique carbon layer structure, so that lithium ions can be inserted and removed from all directions of the sphere, and in the charging process, the lithium ions can be inserted into the carbon layer and can be stored in micropores in the mesocarbon microbeads 1, and the more micropores are, the larger the lithium storage amount is.
According to the composite lithium negative electrode, redundant lithium ions for generating lithium dendrites can be inserted from all directions of the sphere in the charging and discharging process, and the lithium dendrites are prevented from being generated. Meanwhile, the inserted lithium ions can also participate in the reaction of the battery, so that the cycle life of the battery is prolonged.
In some embodiments, the raw material of the mesocarbon microbeads includes any one or more of coal pitch, coal tar, petroleum residual pitch, synthetic resin and synthetic pitch. The mesocarbon microbeads can be synthesized by adding carbon black or iron compound as additive into the raw materials.
In some embodiments, the lithium metal 3 is lithium sheet with a thickness of 5-1100 μm, lithium tape, or lithium metal powder with a particle size of 20-50 μm.
In some embodiments, the molar ratio of the lithium metal 3 to the mesocarbon microbeads is 1:9 to 9: 1.
The second aspect of the present invention provides a method for preparing the lithium composite negative electrode of the solid-state battery, which comprises the following steps:
a) mixing, laminating or adhering the mesocarbon microbeads and the lithium metal 3 to obtain a pretreatment structure;
b) heating, fusing or rolling the pretreatment structure to obtain a lithium cathode;
c) and placing the lithium negative electrode in an environment with a water value less than 1ppm and an oxygen value less than 1ppm for standing to form the composite lithium negative electrode with the composite interface layer 2.
Step a) pretreating the mesocarbon microbeads, and mixing, laminating or adhering the mesocarbon microbeads with the lithium metal 3 after removing water. And b) heating, fusing or rolling the mixed or attached and adhered mesocarbon microbeads and the lithium metal 3. And c) placing the heated and fused or rolled lithium cathode in an environment with the oxygen value less than 1ppm and standing, wherein a conductive and relatively stable lithium-philic layer, namely an interface composite layer, can be formed due to the adsorption and intercalation effects of the metallic lithium 3 and the mesocarbon microbeads 1.
In some embodiments, the rolling pressure in step b) is 0.1 to 100MPa, and the hot melting temperature is 25 to 200 ℃.
In some embodiments, the standing time of step c) is at least 1.5 hours, and the standing temperature is 25-200 ℃.
In some embodiments, the rolling in step b) is performed by any one or more of a roller, a punch or a tablet press; the heating fusion can be performed by using a hot melting cavity.
In some embodiments, the theoretical specific capacity of the composite lithium negative electrode is 700-3600 mAh/g.
The third aspect of the invention provides a solid-state battery, which comprises the composite lithium negative electrode or the composite lithium negative electrode prepared by the preparation method.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrations only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the following examples are on a weight basis, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the equipment used in the examples is commercially available.
Example 1
And (3) dewatering the mesocarbon microbeads, mixing the dewatered mesocarbon microbeads with 20 microns of lithium metal powder according to the molar ratio of 2:8, heating and fusing the mixed lithium metal powder and the mesocarbon microbeads at 60 ℃ by adopting a hot melting cavity, and standing for 72 hours in an environment with the water value of 0.5ppm and the oxygen value of 0.5ppm to obtain the composite lithium cathode with the composite interface layer.
In a lithium-lithium symmetrical battery system, (electrolyte: 2% LiNO)31M LiTFSI DOL/DME (volume ratio 1: 1); current density: 1.0mA cm-2(ii) a Circulation capacity: 1.0mAh cm-2) The volume deformation of the lithium-carbon composite interface layer is obviously smaller than the volume change of a pure lithium sheet. In a lithium iron phosphate (LFP) full cell system, (electrolyte: 1M LiPF6EC/DEC (volume ratio 1: 1); circulation capacity: 1.0mAh cm-2) The circulation is stabilized for 200 circles, and the capacity retention rate is more than 80%.
Example 2
And (3) dehydrating the mesocarbon microbeads, adhering the mesocarbon microbeads and the metallic lithium in a molar ratio of 4:6, rolling the adhered mesocarbon microbeads and the metallic lithium by using a roller mill, placing the rolled mesocarbon microbeads and the metallic lithium in an environment with a water value of 0.7ppm and an oxygen value of 0.7ppm, and standing the rolled mesocarbon microbeads and the metallic lithium for 72 hours to obtain the composite lithium cathode with the composite interface layer.
In a full cell system of lithium iron phosphate (LFP), (electrolyte: 1M LiPF)6EC/DEC (volume ratio 1: 1); circulation capacity: 1.0mAh cm-2) Circulating for 180 circles stably, and keeping the capacity at more than 80%.
Example 3
And (3) dehydrating the mesocarbon microbeads, adhering the mesocarbon microbeads and the metallic lithium according to the molar ratio of 6:4, rolling the adhered mesocarbon microbeads and the metallic lithium by a punching machine, placing the rolled mesocarbon microbeads and the metallic lithium in an environment with the water value of 0.8ppm and the oxygen value of 0.8ppm, and standing for 72 hours to obtain the composite lithium cathode with the composite interface layer.
In a lithium iron phosphate (LFP) full cell system, (electrolyte: 1M LiPF6EC/DEC (volume ratio 1: 1); circulation capacity: 1.0mAh cm-2) The circulation is stable for 157 circles, and the capacity retention rate is over 80 percent.
Example 4
And (3) dehydrating the mesocarbon microbeads, adhering the mesocarbon microbeads and the metallic lithium according to the molar ratio of 8:2, heating and fusing the mixed metallic lithium powder and the mesocarbon microbeads at 200 ℃ by adopting a hot melting cavity, placing the fused metallic lithium powder and the mesocarbon microbeads in an environment with the water value of 0.6ppm and the oxygen value of 0.6ppm, and standing for 72 hours to obtain the composite lithium cathode with the composite interface layer.
Lithium iron phosphate (LFP)In the full cell system, (electrolyte: 1M LiPF)6EC/DEC (volume ratio 1: 1); circulation capacity: 1.0mAh cm-2) The circulation is stable for 157 circles, and the capacity retention rate is over 80 percent.
While the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. The composite lithium cathode of the solid-state battery is characterized by comprising metallic lithium and a plurality of interphase carbon microspheres which are arranged at intervals, wherein part of each interphase carbon microsphere is inserted into the metallic lithium to form a composite interface layer; the thickness of the composite lithium negative electrode is 100-1500 mu m.
2. The composite lithium negative electrode of the solid-state battery according to claim 1, wherein the raw material of the mesocarbon microbeads includes any one or more of coal pitch, coal tar, petroleum residual pitch, synthetic resin, and synthetic pitch.
3. The composite lithium negative electrode of the solid-state battery according to claim 1, wherein the metallic lithium is a lithium sheet having a thickness of 5 to 1100 μm, a lithium ribbon, or a metallic lithium powder having a particle size of 20 to 50 μm.
4. The composite lithium negative electrode of the solid-state battery according to claim 1, wherein the molar ratio of the metallic lithium to the mesocarbon microbeads is 1:9 to 9: 1.
5. A method for preparing a composite lithium negative electrode for a solid-state battery according to any one of claims 1 to 4, characterized by comprising the steps of:
a) mixing, laminating or adhering the mesocarbon microbeads and the lithium metal to obtain a pretreatment structure;
b) heating, fusing or rolling the pretreatment structure to obtain a lithium cathode;
c) and placing the lithium negative electrode in an environment with a water value less than 1ppm and an oxygen value less than 1ppm for standing to form the composite lithium negative electrode with a composite interface layer.
6. The preparation method of claim 5, wherein the rolling pressure in the step b) is 0.1-100 MPa, and the hot melting temperature is 25-200 ℃.
7. The preparation method of claim 5, wherein the standing time of the step c) is at least 1.5h, and the standing temperature is 25-200 ℃.
8. The method according to claim 5, wherein the rolling in step b) is performed by any one or more of a roller, a punch, or a tablet press.
9. The preparation method according to claim 5, wherein the theoretical specific capacity of the composite lithium negative electrode is 700-3600 mAh/g.
10. A solid-state battery comprising the composite lithium negative electrode according to any one of claims 1 to 4 or the composite lithium negative electrode produced by the method according to any one of claims 5 to 9.
CN202210545349.8A 2022-05-19 2022-05-19 Composite lithium cathode of solid-state battery, preparation method of composite lithium cathode and solid-state battery Pending CN114784281A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000323127A (en) * 1990-11-22 2000-11-24 Osaka Gas Co Ltd Lithium secondary battery
CN102354759A (en) * 2011-11-04 2012-02-15 上海空间电源研究所 Lithium negative pole, preparation method thereof and battery comprising lithium negative pole
CN102867983A (en) * 2011-07-04 2013-01-09 中国人民解放军63971部队 Nonaqueous secondary lithium battery
CN105845891A (en) * 2016-05-13 2016-08-10 清华大学 Metal lithium negative electrode with dual-layer structure
CN109686921A (en) * 2018-11-21 2019-04-26 清华大学 A kind of composition metal cathode of lithium and preparation method thereof with lithium carbon compound interface layer
CN110931712A (en) * 2019-12-10 2020-03-27 清华大学 Composite metal lithium cathode with filler and preparation method thereof
US20200123008A1 (en) * 2017-07-26 2020-04-23 China Energy Cas Technology Co., Ltd. Carbon nanoparticle-porous skeleton composite material, its composite with lithium metal, and their preparation methods and use

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000323127A (en) * 1990-11-22 2000-11-24 Osaka Gas Co Ltd Lithium secondary battery
CN102867983A (en) * 2011-07-04 2013-01-09 中国人民解放军63971部队 Nonaqueous secondary lithium battery
CN102354759A (en) * 2011-11-04 2012-02-15 上海空间电源研究所 Lithium negative pole, preparation method thereof and battery comprising lithium negative pole
CN105845891A (en) * 2016-05-13 2016-08-10 清华大学 Metal lithium negative electrode with dual-layer structure
US20200123008A1 (en) * 2017-07-26 2020-04-23 China Energy Cas Technology Co., Ltd. Carbon nanoparticle-porous skeleton composite material, its composite with lithium metal, and their preparation methods and use
CN109686921A (en) * 2018-11-21 2019-04-26 清华大学 A kind of composition metal cathode of lithium and preparation method thereof with lithium carbon compound interface layer
CN110931712A (en) * 2019-12-10 2020-03-27 清华大学 Composite metal lithium cathode with filler and preparation method thereof

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Application publication date: 20220722