CN110085852A - Conductive structure and electrode - Google Patents

Conductive structure and electrode Download PDF

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Publication number
CN110085852A
CN110085852A CN201910450331.8A CN201910450331A CN110085852A CN 110085852 A CN110085852 A CN 110085852A CN 201910450331 A CN201910450331 A CN 201910450331A CN 110085852 A CN110085852 A CN 110085852A
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shell
conductive structure
kernel
metal
structure according
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CN110085852B (en
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康帅
陆文强
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Chongqing Institute of Green and Intelligent Technology of CAS
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Chongqing Institute of Green and Intelligent Technology of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • 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
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention provides a kind of conductive structure and electrode, for solving the problems, such as that electric conductivity is bad in the prior art.The present invention provides a kind of conductive structure, comprising: shell, the shell are hard structure, and the shell is spherical shape；Kernel, the kernel are located in the shell, and the kernel is rigid conductive structure, and the fusing point of the kernel is lower than the fusing point of the shell；The kernel can partially and outer casing inner wall contact, the kernel contact area account for 10% or more of the shell surface area.

Description

Conductive structure and electrode
Technical field
The present invention relates to conductive material fields, more particularly to a kind of conductive structure and electrode.
Background technique
Lithium ion needed for shell mechanism material and electronics are transmitted by shell, and electrolyte does not connect directly with active material Touching, therefore, can establish stable solid/liquid interfaces, it is ensured that stable cycle performance.This structure is characterized in: firstly, shell It is usually relatively thin, faster charge transmission may be implemented；Hollow shell structure is to solve high-capacity cathode material by volume expansion institute One of the electrochemistry of cause-mechanical property decline most effective solution of problem, existing kernel is circle, and kernel and shell connect The problem of contacting surface product is small, this structure is once shell interfaces combine deficiency, it will extend the transmission path of electronics and lithium ion, And then lead to the decline of battery high rate performance.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of conductive structure and electrodes, use In solving the problems, such as that electric conductivity is bad in the prior art.
In order to achieve the above objects and other related objects, the present invention provides a kind of conductive structure, comprising:
Shell, the shell are hard structure, and the shell is spherical shape；
Kernel, the kernel are located in the shell, and the kernel is rigid conductive structure, and the fusing point of the kernel is lower than The fusing point of the shell；
The kernel can partially and outer casing inner wall contact, the kernel contact area account for the shell own face Long-pending 10% or more.
Optionally, the shell be carbon material be made or titanyl compound be made and/or the inner nuclear material by metal, Silicon, silica or silicon alloy are made.
Optionally, the shell is equipped with several micropores, and the inner and outer wall of shell described in the microporous connectivity is described outer The contact surface of shell is equipped with several protruding portions, and the protruding portion is embedded into the micropore of part.
Optionally, the thickness range of the shell is 1 nanometer to 200 nanometers.
Optionally, the interior Assessment of Nuclear Volume and the ratio of the shell inner volume are 1:1.5 to 1:4.
Optionally, chain is conspired to create by linear structure connection before each shell.
Optionally, the linear structure is made of carbon material, metal or metal oxide, and the linear structure is hollow Structure or solid construction.
Optionally, the linear structure includes carbon pipe, and the carbon pipe is equipped with several micropores.
Optionally, equipped with metal, perhaps the metal oxide metal or metal oxide are filled out completely in the carbon pipe Fill or be not filled up completely the carbon pipe.
A kind of electrode, including the conductive structure；
Cathode of the conductive structure as lithium ion battery, alternatively, anode of the conductive structure as lithium-sulfur cell, Perhaps cathode or conductive structure cathode as kalium ion battery of the conductive structure as sodium-ion battery.Such as Upper described, conductive structure and electrode of the invention at least have the advantages that
Increase its electric conductivity so that the contact area of kernel and shell becomes larger by the setting of contact surface and non-contact face Energy.
Detailed description of the invention
Fig. 1 is shown as the schematic diagram of existing conductive structure.
Fig. 2 is shown as a kind of schematic diagram of embodiment of conductive structure of the invention.
Fig. 3 is shown as the schematic diagram of conductive structure another embodiment of the invention.
Component label instructions
1 shell
2 kernels
3 linear structures
Specific embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation Content disclosed by book is understood other advantages and efficacy of the present invention easily.
It please refers to Fig.1 to Fig.3.It should be clear that this specification structure depicted in this specification institute accompanying drawings, ratio, size etc., only to Cooperate the revealed content of specification, so that those skilled in the art understands and reads, being not intended to limit the invention can be real The qualifications applied, therefore do not have technical essential meaning, the tune of the modification of any structure, the change of proportionate relationship or size It is whole, in the case where not influencing the effect of present invention can be generated and the purpose that can reach, it should all still fall in disclosed skill In the range of art content can cover.Meanwhile in this specification it is cited as "upper", "lower", "left", "right", " centre " and The term of " one " etc. is merely convenient to being illustrated for narration, rather than to limit the scope of the invention, relativeness It is altered or modified, under the content of no substantial changes in technology, when being also considered as the enforceable scope of the present invention.
Each embodiment is only for the purpose of illustration below.Between each embodiment, it can be combined, not only limit In the content that following single embodiment shows.
In Fig. 1, conductive structure includes shell 1 and kernel 2, but its kernel is spherical structure, and kernel and shell Contact area is smaller, and electric conductivity is poor.
In the present embodiment, Fig. 2 to Fig. 3 is please referred to, the present invention provides a kind of conductive structure, comprising: shell 1 and kernel 2, institute Stating shell 1 is hard structure, and the shell 1 is spherical shape, does not set micropore on the shell 1, and institute's kernel 2 is located in the shell 1, The kernel 2 is rigid conductive structure, such as metal, silicon, silica or silicon alloy, metal its can specifically be selected as Sn, Al, Ge etc., silicon alloy can specifically be selected as silico-aluminum, manganese-silicon, Li-Si alloy etc., and the fusing point of the kernel 2 is outer lower than described The fusing point of shell 1；The kernel 2 can partially and 1 inner wall of shell contact, 2 contact area of kernel account for the shell 1 certainly 10% or more of body surface area specifically can be 10%, 20%, 30%, 40%, 50% etc., and the shape of kernel 2 can be flat The structures such as structure, oval structure, herein without limitation to shape, kernel 2 are collapsed in shell 1, the contact of kernel 2 and shell 1 Area is larger, for lithium ion battery, can stablize solid/liquid interfaces, can buffer body caused by a large amount of lithium ion insertions Product variation, improves charge/discharge capacity and stable circulation performance；1 interface cohesion of shell is good, can provide to lithium ion and electronics Smooth transmission channel improves high rate performance.Since the fusing point of shell 1 is higher than the fusing point of kernel 2, so that being carried out to kernel 2 When manufacture, shell 1 and kernel 2 can be heated together, when kernel 2, which softens, to collapse, shell 1 can hold its shape, and realize The increase of contact area, while also assuring support effect, manufacture also facilitates.
In the present embodiment, Fig. 2 to Fig. 3 is please referred to, the shell 1 is equipped with several micropores, outer described in the microporous connectivity The inner and outer wall of shell 1, the contact surface are equipped with several protruding portions, and the protruding portion is embedded into the micropore of part.If Setting micropore can be manufactured by the way of chemical etching, and when manufacture can coat 1 layer of shell on an metal oxide, then be used Acid solution or etching alkaline solution, several micropores at 1 layer of shell upper etching, and the oxygen of acid solution or aqueous slkali and kernel 2 Change layer contact, the oxide layer of kernel 2 is removed to form metal inner core 2, then uses again and it is heated, so that kernel 2 Metal softening collapses, and since the fusing point of shell 1 is higher than the fusing point of kernel 2, shell 1 is undeformed at this time, and kernel 2 collapses, Contact area becomes larger, and easily manufactured.
In the present embodiment, Fig. 2 to Fig. 3 is please referred to, the shell 1 is that carbon material is made or titanyl compound is made.Carbon Material is specifically as follows graphene, amorphous carbon etc., and fusing point is higher, even if at a higher temperature, being also not easy to soften, energy Enough play good support effect.
In the present embodiment, Fig. 2 to Fig. 3 is please referred to, the thickness range of the shell 1 is 1 nanometer to 200 nanometers, specifically may be used To be 1 nanometer, 10 nanometers, 50 nanometers, 70 nanometers, 100 nanometers, 110 nanometers, 150 nanometers, 170 nanometers, 200 nanometers etc..It is too small Structural instability, too thick lithium ion transport performance can be poor.
In the present embodiment, Fig. 2 to Fig. 3 is please referred to, the ratio of 1 inner volume of 2 volume of kernel and the shell arrives for 1:1.5 1:4 is specifically as follows 1:1.5,1:1.8,1:2,1:2.5,1:3,1:3.5,1:4 etc., there is enough skies between shell 1 and kernel 2 Gap is to accommodate the volume expansion of kernel 2, to guarantee stable cycle performance.
In the present embodiment, referring to Fig. 3, conspiring to create chain by the connection of linear structure 3 before each shell 1.Pass through One-dimentional structure further speeds up electronics transfer, and the continuous variation of the deintercalation with lithium ion, material internal tension is inhibited to draw The conductive additive risen regroups or collapses, to further improve the high rate performance and stable circulation performance of material.
In the present embodiment, the linear structure 3 is made of carbon material, and carbon material is specifically as follows graphene, amorphous carbon It is solid construction Deng, the linear structure 3.
In the present embodiment, the linear structure 3 is made of carbon material, and carbon material is specifically as follows graphene, amorphous carbon It is hollow structure Deng, the linear structure 3.
In the present embodiment, the linear structure 3 is made of metal, and the linear structure 3 is hollow structure.
In the present embodiment, the linear structure 3 is made of metal, and the linear structure 3 is solid construction.
In the present embodiment, the linear structure 3 is made of metal oxide, and the linear structure 3 is hollow structure.
In the present embodiment, the linear structure 3 is made of metal oxide, and the linear structure 3 is solid construction.
In the present embodiment, the linear structure 3 includes carbon pipe, and the carbon pipe is equipped with several micropores.Hollow carbon pipe knot Structure, electric conductivity get a promotion, by the way that several micropores are arranged so that it is when manufacturing carbon pipe, can using ZnO as substrate, A certain amount of polymer of applied atop, then by heat treatment polymer carbonization.Polymer can choose furfuryl alcohol, pyrroles etc., Then it is performed etching using acid & alkali liquid, forms several micropores on carburization zone, then internal ZnO is carved again Erosion, facilitates manufacture.
Being equipped with metal in the present embodiment, in the carbon pipe, perhaps the metal oxide metal or metal oxide are complete Full packing is not filled up completely the carbon pipe.
A kind of electrode, including the conductive structure；
Cathode of the conductive structure as lithium ion battery, alternatively, anode of the conductive structure as lithium-sulfur cell, Perhaps cathode or conductive structure cathode as kalium ion battery of the conductive structure as sodium-ion battery.
When it is specifically used as electrode structure, it can be coated on the electrode by bonding agent.
In conclusion the present invention stablizes solid/liquid interfaces, volume change caused by a large amount of lithium ion insertions can be buffered, is mentioned High charge-discharge capacity and stable circulation performance；1 interface cohesion of shell is good, can mention to lithium ion or other ions and electronics For smooth transmission channel, high rate performance is improved.The chain structure of 1 particle of hollow shell, by one-dimentional structure, further plus Fast electronics transfer, and inhibit to lead caused by the deintercalation with lithium ion or other ions, the continuous variation of material internal tension Electric additive regroups or collapses, to further improve the high rate performance and stable circulation performance of material.So this Invention effectively overcomes various shortcoming in the prior art and has high industrial utilization value.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as At all equivalent modifications or change, should be covered by the claims of the present invention.

Claims (10)

1. a kind of conductive structure characterized by comprising
Shell, the shell are hard structure, and the shell is spherical shape；
Kernel, the kernel are located in the shell, and the kernel is rigid conductive structure, and the fusing point of the kernel is lower than described The fusing point of shell；
The kernel can partially and outer casing inner wall contact, the kernel contact area account for the shell surface area 10% or more.
2. conductive structure according to claim 1, it is characterised in that: the shell is made for carbon material or the oxidation of titanium Object is made and/or the inner nuclear material is made of metal, silicon, silica or silicon alloy.
3. conductive structure according to claim 1, it is characterised in that: the shell is equipped with several micropores, the micropore It is connected to the inner and outer wall of the shell, the contact surface of the kernel is equipped with several protruding portions, and the protruding portion is embedded into portion Divide in the micropore.
4. conductive structure according to claim 1, it is characterised in that: the thickness range of the shell is 1 nanometer and receives to 200 Rice.
5. conductive structure according to claim 1, it is characterised in that: the ratio of the interior Assessment of Nuclear Volume and the shell inner volume For 1:1.5 to 1:4.
6. -5 any conductive structure according to claim 1, it is characterised in that: pass through linear knot before each shell Structure connection conspires to create chain.
7. conductive structure according to claim 6, it is characterised in that: the linear structure is by carbon material, metal or gold Belong to oxide to be made, the linear structure is hollow structure or solid construction.
8. conductive structure according to claim 7, it is characterised in that: the linear structure includes carbon pipe, on the carbon pipe Equipped with several micropores.
9. conductive structure according to claim 8, it is characterised in that: be equipped with metal in the carbon pipe or metal aoxidizes Object, the metal or metal oxide are filled up completely or are not filled up completely the carbon pipe.
10. a kind of electrode, it is characterised in that:
Including any conductive structure of claim 1-9；
Cathode of the conductive structure as lithium ion battery, alternatively, anode of the conductive structure as lithium-sulfur cell, or Cathode or conductive structure cathode as kalium ion battery of the conductive structure as sodium-ion battery.
CN201910450331.8A 2019-05-28 2019-05-28 Conductive structure and electrode Active CN110085852B (en)

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CN109309221A (en) * 2018-09-29 2019-02-05 盐城师范学院 A kind of preparation method of silicon particle/graphene quantum dot core-shell structure
CN209804803U (en) * 2019-05-28 2019-12-17 中国科学院重庆绿色智能技术研究院 Conductive structure and electrode

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CN116936816A (en) * 2023-09-19 2023-10-24 深圳市贝特瑞新能源技术研究院有限公司 Skeleton composite material, preparation method thereof, negative plate and battery
CN116936816B (en) * 2023-09-19 2023-11-17 深圳市贝特瑞新能源技术研究院有限公司 Skeleton composite material, preparation method thereof, negative plate and battery

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