CN109904523A - The manufacturing method of sulfide solid battery - Google Patents

The manufacturing method of sulfide solid battery Download PDF

Info

Publication number
CN109904523A
CN109904523A CN201811186908.0A CN201811186908A CN109904523A CN 109904523 A CN109904523 A CN 109904523A CN 201811186908 A CN201811186908 A CN 201811186908A CN 109904523 A CN109904523 A CN 109904523A
Authority
CN
China
Prior art keywords
sulfide solid
cathode
lithium
active material
battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201811186908.0A
Other languages
Chinese (zh)
Other versions
CN109904523B (en
Inventor
濑上正晴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyota Motor Corp
Original Assignee
Toyota Motor Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyota Motor Corp filed Critical Toyota Motor Corp
Publication of CN109904523A publication Critical patent/CN109904523A/en
Application granted granted Critical
Publication of CN109904523B publication Critical patent/CN109904523B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/48—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
    • H01M4/36—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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The project of the application is in the case where cathode agent of the surface of the negative electrode collector of the cupric stacking comprising silicon-based active material and sulfide solid electrolyte constitutes cathode, react sulfide solid electrolyte with copper in the OCV of silicon-based active material, copper spreads that the slight short circuit of positive electrode and negative electrode occurs from negative electrode collector to side of the positive electrode via sulfide solid electrolyte.The solution of the application is to spread lithium to silicon-based active material when making cathode agent, reduce current potential.Specifically, by selected from graphite and lithium titanate one of in material elements doped lithium and obtain the 1st process of pre-doping material, sulfide solid electrolyte and silicon-based active material and the pre-doping material be obtained by mixing to the 2nd process of cathode agent and the surface of the negative electrode collector in cupric is laminated the cathode agent and obtains the 3rd process of cathode, manufacture sulfide solid battery.

Description

The manufacturing method of sulfide solid battery
Technical field
This application involves the manufacturing methods of sulfide solid battery.
Background technique
Patent Documents 1 to 3 disclose it is a kind of have anode, cathode and be set between positive electrode and negative electrode solid electricity Solve the sulfide solid battery of matter layer.In technology disclosed in patent document 1, sulfide solid electrolyte, silicon systems activity will be included The cathode agent of substance and active carbon material, is laminated in the surface for the negative electrode collector being made of copper, to obtain cathode.Specially In technology disclosed in sharp document 2, during using voltage of battery is reached in the primary charging of sulfide solid battery, from Anode supplies lithium to cathode, in the negative active material elements doped lithium.It will include sulfide in technology disclosed in patent document 3 The cathode agent of solid electrolyte is laminated in front of the surface of negative electrode collector, and sulfidation-resistance is arranged on the surface of negative electrode collector Layer.
Citation
Patent document 1: Japanese Unexamined Patent Publication 2017-054720 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2017-147158 bulletin
Patent document 3: International Publication No. 2014/156638
Summary of the invention
The lithium normal potential of the electrode of sulfide solid battery is equal with the OCV of the active material before charge and discharge.For example, In the case that cathode agent comprising silicon-based active material is laminated in the surface of negative electrode collector to constitute cathode, cathode tool There is the lithium normal potential of about 2.8V.
On the other hand, the opinion of people according to the present invention will include that the cathode agent of sulfide solid electrolyte is laminated in In the case that the surface of negative electrode collector comprising copper is to constitute cathode, in the current potential for being lower than 2.8V, sulfide solid electrolysis Matter is reacted with copper, generates conductive CuS etc..
It i.e., will include that the cathode agent of silicon-based active material and sulfide solid electrolyte is laminated in the cathode comprising copper In the case that the surface of collector is to constitute cathode, in the OCV of silicon-based active material, sulfide solid electrolyte is anti-with copper It answers, copper is spread via sulfide solid electrolyte from negative electrode collector to side of the positive electrode.Sulfide is being manufactured using such cathode In the case where solid state battery, it is possible to self discharge as caused by the micro-short circuit of positive electrode and negative electrode etc. occur.
The application discloses a kind of manufacturer of sulfide solid battery as one of means for solving the problem Method has following process: the 1st process, selected from graphite and lithium titanate at least one of elements doped lithium in material, obtain pre- Dopant material；Sulfide solid electrolyte, silicon-based active material and the pre-doping material are mixed, obtain cathode by the 2nd process Mixture；And the 3rd process, the cathode agent is laminated on the surface of the negative electrode collector of cupric, obtains cathode.
In the manufacturing method of the disclosure, the lithium that is adulterated in the pre-doping material that preferably makes the cathode agent include The ratio between the capacity conversion value (X) of total amount, the total capacity (Y) of the silicon-based active material for including with the cathode agent (X/Y) As 0.0005 or more.
In the manufacturing method of the disclosure, preferably in the 1st process, using the electrochemical reaction in lithium ion battery, Elements doped lithium in the material.
In the manufacturing method of the disclosure, scheduled pre-doping material is mixed with silicon systems active matter, makes cathode agent.It should In the case of, after just production cathode agent, lithium is spread from pre-doping material to silicon-based active material, in the case where cathode Current potential reduces.I.e., it is able to suppress reacting for sulfide solid electrolyte and copper, is able to suppress copper via sulfide solid electrolyte It is spread from negative electrode collector to side of the positive electrode, is able to suppress self discharge as caused by the micro-short circuit of positive electrode and negative electrode etc..In addition, due to Pre-doping material is present in cathode with conductive and/or ionic conductivity state, and therefore, it is difficult to become battery behavior Negative effect.
Detailed description of the invention
Fig. 1 is the figure for the process for illustrating the manufacturing method S10 of sulfide solid battery 100.
Fig. 2 is the skeleton diagram for the process for illustrating the manufacturing method S10 of sulfide solid battery 100.
Fig. 3 is the skeleton diagram for illustrating the structure of sulfide solid battery 100.
Description of symbols
10 cathode
1 material made of graphite and/or lithium titanate
2 pre-doping materials
3 sulfide solid electrolytes
4 silicon-based active materials
5 cathode agents
6 negative electrode collectors
20 anodes
21 positive electrode collectors
22 positive electrode material mixture layers
30 solid electrolyte layers
100 sulfide solid batteries
Specific embodiment
1. the manufacturing method of sulfide solid battery
Referring to Fig.1~3, the process of the manufacturing method S10 of sulfide solid battery 100 is illustrated.Sulfide solid The manufacturing method S10 of battery 100 has following process: the 1st process S1, selected from graphite and lithium titanate at least one of material Elements doped lithium in material 1, obtains pre-doping material 2；2nd process S2 is mixed sulfide solid electrolyte 3, silicon-based active material 4 and in advance Miscellaneous material 2 mixes, and obtains cathode agent 5；And the 3rd process S3, cathode agent is laminated on the surface of the negative electrode collector 6 of cupric 5, obtain cathode 10.
1.1. the 1st process
As shown in Fig. 2 (A), in the 1st process S1, selected from graphite and lithium titanate at least one of mix in material 1 Miscellaneous lithium obtains pre-doping material 2.
1.1.1. material 1
Material 1 by selected from graphite and lithium titanate (LTO) at least one of be made.Graphite, lithium titanate are all that can inhale The material of hiding and release lithium, it is known that can be used as the negative electrode active material of lithium ion battery.The case where graphite is compared with LTO Under, preferred graphite.This is because the cathode potential of graphite is low, keep the technical effect of the disclosure more obvious.In addition, being also due to The capacity of graphite is big.In addition, due also to graphite can play high-performance as conductive auxiliary agent.Graphite can be electrographite can also To be natural graphite.The composition of lithium titanate is not particularly limited, such as preferred Li4Ti5O12.For the shape of material 1 It is not particularly limited, particularly preferably particle shape.
1.1.2. the doping method of lithium
The method for obtaining pre-doping material 2 about the elements doped lithium in material 1, can use various methods.For example, can lift Out and material 1 and lithium source are carried out physical mixed in material 1 method of elements doped lithium, be electrochemically inserted into material 1 The method etc. of lithium.From the viewpoint of it can easily control the lithium amount adulterated to material 1, preferably by lithium ion battery Electrochemical reaction and in material 1 elements doped lithium.For example, it is preferable to by material 1, in the current potential higher than material 1 by lithium ion charge and discharge Positive active material and electrolyte combination appropriate with lithium-ion-conducting, to constitute lithium ion battery, and benefit With the charging reaction in the lithium ion battery, the elements doped lithium in material 1.The lithium ion battery used in this case can be liquid system Battery is also possible to solid state battery.The sight of pre-doping material 2 can be especially easily separated after elements doped lithium from material 1 Point etc. sets out, it is preferable to use liquid system battery (nonaqueous electrolytic solution system battery, water system battery).I.e., preferably by material 1, than material Expect 1 high current potential by the positive active material of lithium ion charge and discharge, electrolyte (such as the LiPF with lithium-ion-conducting6 Deng) and for combining the solvent (water, organic solvent) of the electrolyte dissolution, constitute the lithium ion battery of liquid system, and benefit With the charging reaction in the lithium ion battery, the elements doped lithium in material 1.Using the electrochemical reaction in lithium ion battery in material In 1 after elements doped lithium, such as lithium ion battery decomposed, peel pre-doping material 2 off, carries out pre-doping material 2 as needed Cleaning crushes.
The lithium amount adulterated to material 1 is not particularly limited.More increase the lithium amount adulterated to material 1, can more subtract The amount of pre-doping material 2 in few aftermentioned cathode agent 5.It is adulterated in material 1 using the charging reaction in lithium ion battery In the case where lithium, elements doped lithium is until charge volume is as 10mAh/g or more preferably in material 1.More preferably 50mAh/g or more, Further preferably 80mAh/g or more, particularly preferably 100mAh/g or more.The upper limit is not particularly limited, preferably 200mAh/g hereinafter, more preferably 180mAh/g hereinafter, further preferably 150mAh/g or less.Alternatively, utilizing lithium-ion electric Charging reaction in pond preferably charges until SOC is preferably 5% or more, more preferably in material 1 in the case where elements doped lithium For until 8% or more, further preferably until 10% or more.The upper limit is not particularly limited, preferably carries out charging straight Become 50% or less to SOC.
1.2. the 2nd process
As shown in Fig. 2 (B), in the 2nd process S2, by sulfide solid electrolyte 3, silicon-based active material 4 and pre-doping Material 2 mixes, and obtains cathode agent 5.
1.2.1. sulfide solid electrolyte 3
Sulfide solid electrolyte 3 can be employed as the sulfide that the solid electrolyte of sulfide solid battery is applicable in. Such as Li can be enumerated2S-P2S5、Li2S-SiS2、LiI-Li2S-SiS2、LiI-Si2S-P2S5、LiI-LiBr-Li2S-P2S5、LiI- Li2S-P2S5、LiI-Li2O-Li2S-P2S5、LiI-Li2S-P2O5、LiI-Li3PO4-P2S5、Li2S-P2S5-GeS2Deng.These it In, it especially more preferably include Li2S-P2S5Sulfide solid electrolyte.A kind of sulfide solid can individually be used only to be electrolysed Matter 3 can also be used in mixed way two or more.In the 2nd process S2, for the amount of sulfide solid electrolyte 3, there is no special It limits, is suitably determined according to the performance of target battery.For example, by the entirety of cathode agent 5 (in the case where wet mixed It is that solid component after removing the drying of solvent is whole, same as below) 100 mass % are set as, preferably sulfide solid is electrolysed The content of matter 3 is set as 10 mass % or more and 60 mass % or less.Lower limit is more preferably 20 mass % or more, and the upper limit is more preferably 50 mass % or less.
1.2.2. silicon-based active material 4
As long as silicon-based active material 4 is used as cathode comprising Si as constitution element and in sulfide solid battery The substance that active material plays a role.It is, for example, possible to use at least one among Si, Si alloy and Si oxide Kind.Particularly preferred Si or Si oxide.The shape of silicon-based active material 4 is not particularly limited.For example, it is preferable to be particle Shape.In the 2nd process S2, the amount of silicon-based active material 4 is not particularly limited, it is suitably true according to the performance of target battery It is fixed.For example, the entirety of cathode agent 5 is set as 100 mass %, the content of silicon-based active material 4 is preferably set as 30 matter Measure % or more and 90 mass % or less.Lower limit is more preferably 50 mass % or more, and the upper limit is more preferably 80 mass % or less.
1.2.3. pre-doping material 2
In the 2nd process S2, the amount of pre-doping material 2 is not particularly limited, according to the lithium in the 1st process S1 Doping etc. is suitably determined.Especially in the 2nd process S2, it is preferable to determine pre-doping materials 2 and silicon-based active material 4 Mixing ratio, so that the capacity conversion value (X) and cathode of the total amount of the lithium adulterated in the pre-doping material 2 that cathode agent 5 includes The ratio between the total capacity (Y) for the silicon-based active material 4 that mixture 5 includes (X/Y) becomes 0.0005 or more.More preferably than (X/Y) 0.0008 or more.The opinion of people according to the present invention can make the lithium of sufficient amount to silicon if being 0.0005 or more than (X/Y) It is that active material 4 is spread, the self discharge in the case where constituting sulfide solid battery 100 can be further suppressed.
Furthermore " the capacity conversion value (X) of the total amount of the lithium adulterated in the pre-doping material 2 that cathode agent 5 includes " refers to, The total amount for the lithium that can be spread from pre-doping material 2 to silicon-based active material 4 in cathode agent 5 is scaled obtained from capacity Value.In the case that using the charging reaction of lithium ion battery, elements doped lithium is in material 1 to obtain pre-doping material 2, Ke Yigen Capacity conversion value (X) is found out according to charge volume (Ah/g)." total capacity (Y) for the silicon-based active material 4 that cathode agent 5 includes " is Refer to, capacity possessed by the silicon-based active material 4 for the uncharged state that cathode agent 5 includes.Specifically, can in addition prepare For measuring the mixture of Y, what the primary charging capacity obtained when being set as according to using to the progress charge and discharge of electrode Li battery obtained Active material charging capacity.
1.2.4. other ingredients
In the 2nd process S2, preferably in the range of being able to solve the above subject, further mixed in cathode agent 5 Conductive auxiliary agent.Conductive auxiliary agent can be employed as material well known to the conductive auxiliary agent used in sulfide solid battery.For example, can With use acetylene black (AB), Ketjen black (KB), vapor phase method carbon fiber (VGCF), carbon nanotube (CNT), carbon nano-fiber (CNF), The carbon materials such as graphite；Nickel, aluminium, stainless steel and other metal materials.Particularly preferred carbon material.Conductive auxiliary agent can individually be used only one Kind, it can also be used in mixed way two or more.The shape of conductive auxiliary agent can be using the various shapes such as powdered, fibrous.The 2nd In process S2, the amount of conductive auxiliary agent is not particularly limited, is suitably determined according to the performance of target battery.For example, The solid component of cathode agent 5 is integrally set as 100 mass %, the content of conductive auxiliary agent is preferably set as 0.5 mass % or more And 20 below mass %.Lower limit is more preferably 1 mass % or more, and the upper limit is more preferably 10 mass % or less.
In the 2nd process S2, preferably in the range of being able to solve the above subject, further mixed in cathode agent 5 Adhesive.Adhesive can be employed as material well known to the adhesive used in sulfide solid battery.It is, for example, possible to use Selected from styrene butadiene ribber (SBR), carboxymethyl cellulose (CMC), acrylonitrile butadiene rubber (ABR), butadiene rubber (BR), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) (PTFE) etc. at least one of.In the 2nd process S2, for viscous The amount of mixture is not particularly limited, and is suitably determined according to the performance of target battery.For example, by the solid of cathode agent 5 Ingredient is integrally set as 100 mass %, and the content of adhesive is preferably set as 1 mass % or more and 30 mass % or less.Lower limit is more Preferably 2 mass % or more, the upper limit are more preferably 15 mass % or less.
In the 2nd process S2, it can further be mixed in cathode agent 5 in the range of being able to solve the above subject Solid electrolyte other than sulfide solid electrolyte 3.For example, lanthanum lithium zirconate, LiPON, Li can be mixed1+XAlXGe2-X (PO4)3, Li-SiO system glass, solid oxide electrolytes such as Li-Al-S-O system glass etc..
In the 2nd process S2, it can further be mixed in cathode agent 5 in the range of being able to solve the above subject Negative electrode active material other than silicon-based active material 4.For example, can be with carbon materials such as admixed graphite, hard carbons；Lithium titanate etc. is each Kind oxide；Lithium metal, lithium alloy etc..
1.2.5. mixed method
In the 2nd process S2, for sulfide solid electrolyte 3, silicon-based active material 4 and pre-doping material 2 are mixed Method to which cathode agent 5 be made is not particularly limited.2nd process S2 can be implemented using well known mixed media.2nd Mixing in process S2 can be the wet mixed using solvent, and (powder is each other for the dry type mixing for being also possible to without using solvent Mixing).From can more uniformly mix material, spread lithium preferably from pre-doping material 2 to silicon-based active material 4 From the perspective of, it is preferable to use solvent wet mixed.Specifically, it is preferable that by sulfide solid electrolyte 3, silicon systems active matter Matter 4 and pre-doping material 2 are mixed together with solvent, obtain the cathode agent 5 of slurry or paste-like.For using in this case The type of solvent be not particularly limited.Such as it is preferable to use butyl butyrates, N-Methyl pyrrolidone (NMP).
1.3. the 3rd process
As shown in Fig. 2 (C), in the 3rd process S3, cathode agent 5 is laminated on the surface of the negative electrode collector 6 of cupric, obtains To cathode 10.
1.3.1. the negative electrode collector 6 of cupric
Negative electrode collector 6 includes copper.For example, the metal foil comprising copper or copper alloy, metal mesh can be enumerated.Alternatively, It can be to substrate plating, copper steam-plating or copper alloy.The metal foil (copper foil) being particularly preferably made of copper.For negative electrode collector 6 Thickness be not particularly limited.It such as is preferably 0.1 μm or more and 1mm hereinafter, more preferably 1 μm or more and 100 μm or less.
1.3.2. laminating method
For being not particularly limited to the method for the surface of negative electrode collector 6 stacking cathode agent 5.It can be to cathode collection It is dried after the surface wet coating cathode agent 5 of electric body 6, and is arbitrarily press-formed, thus cathode agent 5 is laminated In the surface of negative electrode collector 6, cathode agent 5 can also be carried out to the extrusion forming of dry type together with negative electrode collector 6, thus Cathode agent 5 is formed on the surface of negative electrode collector 6.In the case where wet type, as described above it is scattered in preferably cathode agent 5 molten Agent is medium, and slurries or paste is made.Furthermore in the case where extrusion forming in the 3rd process S3, due in cathode agent 5 Middle sulfide solid electrolyte 3, silicon-based active material 4 and the contact of pre-doping material 2 are better, therefore lithium can be made more equal It is spread evenly from pre-doping material 2 to silicon-based active material 4, more significant effect can be played.
It is (wet for the thickness of the layer for the cathode agent 5 being laminated on the surface of negative electrode collector 6 by the 3rd process S3 Be in the case where formula remove solvent drying after thickness) be not particularly limited.Such as preferably 0.1 μm or more and 1mm with Under, more preferably 1 μm or more and 100 μm or less.Alternatively, for high capacity, it can also be thicker.Furthermore preferably so that cathode 10 capacity is greater than the mode of the capacity of anode 20, determines the thickness of the layer of cathode agent 5.
As described above, the cathode 10 of sulfide solid battery 100 can be manufactured by process S1~S3.Furthermore in cathode It, can be in the face of the layer of cathode agent 5 and negative electrode collector 6 opposite side (as side of the positive electrode in the case where battery is made in 10 Face) on, the further layer of the setting cathode agent different from cathode agent 5.For example, it may be only as negative electrode active material Layer etc. comprising the active material (such as active carbon material) other than silicon-based active material.
1.4. supplement
As shown in figure 3, other than the cathode 10 that sulfide solid battery 100 manufactures except through above-mentioned operation S1~S3, also Have anode 20 and solid electrolyte layer 30.Positive 20, the manufacturing method of solid electrolyte layer 30 is well known.I.e., sulfide Solid state battery 100 can be manufactured using method same other than having manufacturing method S10.
1.4.1. anode 20
Those skilled in the art can understand the structure of the anode 20 in sulfide solid battery 100, below to an example Son is illustrated.Anode 20 be generally configured with comprising positive active material and the solid electrolyte as any ingredient, adhesive, The positive electrode material mixture layer 22 of conductive auxiliary agent and other additives (tackifier etc.).It is connect additionally, it is preferred that having with the positive electrode material mixture layer 22 The positive electrode collector 21 of touching.
Positive electrode collector 21 is made of metal foil, metal mesh etc..Particularly preferred metal foil.As anode can be constituted The metal of collector may be exemplified stainless steel, nickel, chromium, gold, platinum, aluminium, iron, titanium, zinc etc..Metal foil, substrate can also be plated It applies, these materials is deposited.
Positive active material contained in positive electrode material mixture layer 22 can be employed as the positive-active of sulfide solid battery Material well known to substance.By among well known active material compared with above-mentioned silicon-based active material 4 charge and discharge potential show it is high The substance of current potential is as a positive electrode active material.For example, cobalt acid lithium, lithium nickelate, Li can be used as a positive electrode active material (Ni,Mn,Co)O2(Li1+αNi1/3Mn1/3Co1/3O2), LiMn2O4, spinel-type lithium composite xoide, lithium titanate, phosphate metal lithium (LiMPO4, M be selected from Fe, Mn, Co, Ni at least one of) etc. the oxide containing lithium.Positive active material can be independent Using only one kind, can also be used in mixed way two or more.Positive active material can have lithium niobate, lithium titanate, phosphorus on surface The coatings such as sour lithium.The shape of the positive electrode active material is not particularly limited.For example, it is preferable to be particle shape, film-form.It is right The content of positive active material in positive electrode material mixture layer is not particularly limited, the anode with previous sulfide solid battery The amount of positive active material contained in mixture layer is equal.
Solid electrolyte can be employed as material well known to the solid electrolyte of sulfide solid battery, such as preferably adopt With above-mentioned sulfide solid electrolyte.In the range of can play desired effect, other than sulfide solid electrolyte, It may include the inorganic solid electrolyte other than sulfide solid electrolyte.About conductive auxiliary agent, adhesive, can also using with Same material in cathode 10.One kind can be individually used only in solid electrolyte, conductive auxiliary agent and adhesive, can also It is two or more to be used in mixed way.The shape of solid electrolyte, conductive auxiliary agent is not particularly limited.It such as is preferably particle Shape.The content of solid electrolyte, conductive auxiliary agent and adhesive in positive electrode material mixture layer is not particularly limited, and it is previous The amount of solid electrolyte contained in the positive electrode material mixture layer of sulfide solid battery, conductive auxiliary agent and adhesive is equal.
Have the anode 20 of the above structure, it can be in the solid electrolyte by positive active material and arbitrarily contained, viscous Mixture and conductive auxiliary agent are added in solvent be kneaded the electrod composition for obtaining slurry after, by by the electrod composition The process that is coated on the surface of positive electrode collector and is dried etc. and be easily manufactured.But it is not limited to such wet type Method can also manufacture anode by dry type.In this way in the case where the surface of positive electrode collector forms the positive electrode material mixture layer of sheet, The thickness of positive electrode material mixture layer is for example preferably 0.1 μm or more and 1mm hereinafter, more preferably 1 μm or more and 100 μm or less.
1.4.2. solid electrolyte layer 30
Those skilled in the art can understand the structure of the solid electrolyte layer 30 in sulfide solid battery 100, below One example is illustrated.Solid electrolyte layer 30 includes solid electrolyte and arbitrary adhesive.Solid electrolyte example As preferably used above-mentioned sulfide solid electrolyte.It can be in the range of can play desired effects, in addition to sulfide solid Other than electrolyte, such as include the inorganic solid electrolyte other than sulfide solid electrolyte.Adhesive can suitably select with The same materials'use of above-mentioned adhesive.The content of each ingredient in solid electrolyte layer 30 is as in the past.Solid electricity The shape for solving matter layer 30 is as in the past.The solid electrolyte layer 30 of particularly preferred sheet.The solid electrolyte layer of sheet 30 for example can obtain the electrolyte of slurry solid electrolyte and arbitrary adhesive to be added in solvent to be kneaded After composition, by the electrolyte composition to be coated on to the surface of substrate and is dried or is coated on positive electrode material mixture layer And/or anode mixture layer surface and the processes such as be dried and be easily manufactured.In this case, the thickness of solid electrolyte layer 30 Degree is for example preferably 0.1 μm or more and 300 μm hereinafter, more preferably 0.1 μm or more and 100 μm or less.
1.4.3. other components
Certainly, can have other than cathode 10, anode 20 and solid electrolyte layer 30 in sulfide solid battery 100 Standby necessary terminal, battery case etc..These components be it is well known, herein omit detailed description.
1.5. sulfide solid battery 100
Manufacturing method S10 by the disclosure and the sulfide solid battery 100 manufactured, such as to have following structures special Sign.I.e., a kind of sulfide solid battery 100 has cathode 10, anode 20 and is set between cathode 10 and anode 20 Solid electrolyte layer 30, the cathode 10 have cupric negative electrode collector 6 and be set to negative electrode collector 6 surface by bearing The layer that pole mixture 5 is formed, the cathode agent 5 include sulfide solid electrolyte 3, silicon-based active material 4 and pre-doping material 2, the pre-doping material 2 selected from graphite and lithium titanate at least one of 1 (the preferably material made of graphite of material 1) doped with lithium in.Structure about each component as described above, omit detailed description herein.
As described above, the manufacturing method S10 of the disclosure, prepares scheduled pre-doping material 2, the 2nd in the 1st process S1 Pre-doping material 2 is mixed with silicon-based active material 4 in process S2, makes cathode agent 5.In this case, in just production cathode After mixture 5, lithium is spread from pre-doping material 2 to silicon-based active material 4, as cathode 10 in the case where lithium standard electric potential drop It is low.I.e., it is able to suppress reacting for sulfide solid electrolyte 3 and copper (copper in negative electrode collector 6), is able to suppress copper via sulphur Compound solid electrolyte 3 is spread from negative electrode collector 6 to positive 20 sides, is able to suppress in sulfide solid battery 100 by anode 20 and self discharge caused by the micro-short circuit of cathode 10 etc..In addition, since pre-doping material 2 is with conductive, ionic conductivity State be present in cathode 10, therefore, it is difficult to become sulfide solid battery 100 characteristic negative effect.
2. the supplement of the advantage of the manufacturing method about the disclosure
Furthermore for the silicon-based active material used as negative electrode active material, by before making cathode agent, benefit The preparatory elements doped lithium with the electrochemical reaction in lithium ion battery, can be obtained same effect.But in this case, with above-mentioned Manufacturing method S10 is compared, and needs to be doped a large amount of active material processing etc., from cost aspect and unrealistic.
In addition, being also able to solve life as negative electrode collector by using the material made of metal apart from copper The problem of producing CuS.But in this case, each performance of the batteries such as cycle characteristics reduces sometimes.
3. certification in the market
About sulfide solid battery whether be using the disclosure manufacturing method manufacture battery, such as can use with Lower method confirmation.I.e., in sulfide solid battery, the negative electrode active material of analysis anode and the not opposite part of cathode, observation It is had both by the balance of the positive and negative electrode potential of the battery bring of three-level, thus, it is possible to confirm whether sulfide solid battery is using this The battery of disclosed manufacturing method manufacture.Alternatively, obtaining pre-doping material using the electrochemical reaction in liquid system battery In the case where, SEI can be formed on the surface of pre-doping material.Therefore, pass through graphite contained in confirmation cathode, the table of lithium titanate Whether face has SEI, is also able to confirm that whether sulfide solid battery is the battery manufactured using the manufacturing method of the disclosure.Make For the compound for constituting SEI, LiF, LiCO can be enumerated3, phosphate etc..As the compound for being confirmed whether to have composition SEI Method, can enumerate by TEM-EELS, ICP, EPS carry out elemental analysis, by TOF-SIMS carry out quality analysis and Combine them the analysis etc. carried out.For example, the element in solid electrolyte raw material is not included in this way to fluorine, by confirming only Included in the SEI for being formed in pre-doping material surface, it is able to determine whether to implement the manufacturing method of the disclosure.
Embodiment
1 > of < embodiment
1. the production of sulfide solid battery
1.1. the production of positive active material
Prepare LiNi1/3Mn1/3Co1/3O2Particle (average grain diameter (D50)6μm).Using sol-gal process the particle table Face is coated LiNbO3.Specifically, under atmospheric pressure, it, will using rotational flow apparatus for coating (Powrex corporation SFP-01) Dissolved with equimolar LiOC2H5With Nb (OC2H5)5Ethanol solution be coated on the surface of above-mentioned particle.Adjustment processing the time with So that the thickness of coating becomes 5nm.Then, coated particle is carried out being heat-treated for 1 hour under 350 DEG C, atmospheric pressure, is thus obtained Positive active material.
1.2. positive production
By obtained positive active material and sulfide solid electrolyte (LiI-Li2O-Li2S-P2S5, average grain diameter (D50) 2.5 μm) by quality ratio it is positive active material: sulfide solid electrolyte=75:25 is weighed, and then relative to The positive active material of 100 mass parts weighs the PVDF system adhesive (Wu Yu chemistry corporation) and 6 mass parts of 4 mass parts Acetylene black as conductive auxiliary agent.They are reconciled in butyl butyrate makes solid component become 70 mass %, utilizes blender It is kneaded, obtains positive paste.By the knife coating using applicator by obtained positive paste with weight per unit area For 30mg/cm2It is coated on the aluminium foil with a thickness of 15 μm, it is 3 minutes dry at 120 DEG C, thus obtain having anode on aluminium foil The anode of mixture layer.
1.3. the production of solid electrolyte layer
The sulfide solid electrolyte similar to the above of 95 mass parts and the conduct bonding of 5 mass parts are weighed respectively The butene rubber of agent, they are reconciled in heptane solvent makes solid component become 70 mass %, utilizes ultrasonic wave distributing device (SMT corporation UH-50) is stirred 2 minutes, obtains solid electrolyte paste.The case where using with positive paste same method, It with weight per unit area is 60mg/cm by obtained solid electrolyte paste2It is coated on substrate (aluminium foil), spontaneously dries it Afterwards, 30 minutes dry at 100 DEG C, thus obtain the substrate with solid electrolyte layer.
1.4. the production of cathode
1.4.1. the production of pre-doping material
Particle (average grain diameter (the D of the natural graphite of 99.7 mass parts is weighed respectively50) 15 μm) and 0.3 mass parts Carboxymethyl cellulose, they are reconciled in ion exchange water make solid component become 60 mass %, by planetary mixer into Row is kneaded and obtains paste.Obtained paste is spread evenly across on copper foil using knife coating, it is 5 minutes dry at 120 DEG C, it obtains To electrode.Obtained electrode is struck out into φ 16mm, using as to electrode Li metal, as partition with a thickness of 20 μm PE partition, as electrolyte nonaqueous electrolytic solution (with 1mol/kg in the mixed solvent (EC:DEC=1:1) of EC and DEC Concentration be dissolved with LiPF6 -) production coin battery.The coin battery is charged by charge and discharge device.Charge volume is relative to hard The total weight of graphite contained by coin battery is adjusted to 100mAh/kg.After charging, coin battery is decomposed under an argon atmosphere, is taken Electrode out peels graphite from copper foil with scraper, obtains pre-doping material after EMC cleaning electrode.
1.4.2. the production of cathode agent and the stacking to copper foil
By above-mentioned sulfide solid electrolyte, the particle (average grain diameter (D of silicon50) 6 μm) and pre-doping material with mass ratio It is calculated as sulfide solid electrolyte: the particle of silicon: pre-doping material=45:53.4:1.6 (silicon-based active material: pre-doping material =97:3) it is weighed, and then the particle of the silicon relative to 100 mass parts, weigh the PVDF system adhesive (Wu Yu of 6 mass parts Chemical company's system) and 6 mass parts the acetylene black as conductive auxiliary agent.They are reconciled in butyl butyrate make solid component at It for 70 mass %, is kneaded using blender, obtains the cathode agent of paste.Through the knife coating using applicator by obtained by To paste be spread evenly across on the copper foil with a thickness of 15 μm, it is 3 minutes dry at 120 DEG C, thus obtain having on copper foil negative The cathode of pole mixture layer.
1.5. the stacking of anode, solid electrolyte layer and cathode
It is 1cm that above-mentioned solid electrolyte layer, which is struck out area,2, with 1ton/cm2It is suppressed.In the solid electrolytic of compacting Face (with the face of substrate opposite side) of the side of matter layer is Chong Die above-mentioned positive and with 1ton/cm2It is suppressed.Substrate is peeled, The surface for peeling substrate of solid electrolyte layer is overlapped above-mentioned cathode and with 6ton/cm2It is suppressed, is obtained by anode/solid Laminated body made of electrolyte layer/cathode.Obtained laminated body is sealed in the aluminium laminated film of subsidiary terminal, is commented The sulfide solid battery of valence.The specification of obtained battery is shown in following table 1.
2. the self discharge inspection of sulfide solid battery
As described above, will form conduction if the copper foil as negative electrode collector is reacted with sulfide solid electrolyte Property high CuS, Cu spreads from negative electrode collector to side of the positive electrode, the micro-short circuit of positive electrode and negative electrode occurs, sulfide solid battery Reduce to Voltage Spontaneous.In order to be evaluated this, the self discharge inspection of sulfide solid battery is carried out by following steps. I.e., after sulfide solid battery being charged first (charge condition: 4.4cccv, current rate 2mA, cut-off current 0.1mA), 25 hours are stood in 25 DEG C of thermostat, the voltage Δ V in measurement standing.As a result it is shown in following table 1.
3. cycle characteristics is evaluated
Compared with the case where silicon-based active material is as negative electrode active material is used only, silicon-based active material and carbon system are used In the case where active material, in charge and discharge, the expansion rate as negative electrode active material entirety is mitigated, it can be expected that sulfide The cycle characteristics of solid state battery improves.To confirm the effect, cyclic test is carried out under the following conditions.After calculating 150 circulations Discharge capacity relative to the ratio between first discharge capacity be used as capacity maintenance rate [%].Furthermore in the cyclic test, lead on one side The fixture for crossing incidentally load cell carries out clamping on one side in a manner of uniformly applying the pressure of 5MPa to positive and negative anodes electrode surface It carries out.Show the result in following table 1.
(cyclic test condition)
Charging: 4.4Vcccv, current rate 10mA, cut-off current 0.5mA
Electric discharge: 3.0Vcc, current rate 10mA
Temperature: 25 DEG C
< embodiment 2~4,1 > of comparative example
It is same with embodiment 1 other than changing the mixing ratio of negative electrode active material and pre-doping material as described in Table 1 Sulfide solid battery is made to sample, self discharge inspection and cycle characteristics evaluation are carried out.By the specification of battery, self discharge inspection knot Fruit and cycle characteristics evaluation result are shown in following table 1.
5 > of < embodiment
Other than charge volume when making pre-doping material is changed to 150mAh/g, make similarly to Example 1 Sulfide solid battery carries out self discharge inspection and cycle characteristics evaluation.By the specification of battery, self discharge inspection result and circulation Evaluating characteristics result is shown in following table 1.
6 > of < embodiment
Lithium titanate (average grain diameter (D will be changed to from graphite as the material of pre-doping materials'use50) 2 μm), and pass through Following steps obtain pre-doping material, make sulfide solid battery similarly to Example 1 in addition to this, carry out self discharge inspection It looks into and is evaluated with cycle characteristics.The specification of battery, self discharge inspection result and cycle characteristics evaluation result are shown in following table 1.
The acetylene black of the lithium titanate of 92 mass parts, the PVDF system adhesive of 3 mass parts and 5 mass parts is weighed respectively, it will They reconcile in NMP makes solid component become 70 mass %, is kneaded by planetary mixer, obtains paste.Using with Obtained paste is coated on copper foil and is made it dry by the same knife coating of embodiment 1, obtains electrode.Using obtained Electrode makes coin battery similarly to Example 1, is charged similarly to Example 5 (charge volume 150mAh/g), with reality It applies example 1 and is carried out similarly the decomposition of coin battery and from copper foil after removing, the powder peeled is made to be scattered in about its body In 10 times long-pending of NMP, 3 centrifuge separations are repeated, thus will be attached to the removing such as PVDF system adhesive of lithium titanate.It will The particle obtained after centrifuge separation is as pre-doping material.
7 > of < embodiment
Si oxide (average grain diameter (D is changed to instead of silicon50) 5 μm), and change the weight per unit area of cathode, remove this It makes sulfide solid battery similarly to Example 1 in addition, carries out self discharge inspection and cycle characteristics evaluation.By the rule of battery Lattice, self discharge inspection result and cycle characteristics evaluation result are shown in following table 1.
8 > of < embodiment
Charge volume when making pre-doping material is changed to 10mAh/g, and changes negative electrode active as described in Table 1 The mixing ratio of substance and pre-doping material makes sulfide solid battery similarly to Example 1 in addition to this, carries out self discharge It checks and cycle characteristics is evaluated.The specification of battery, self discharge inspection result and cycle characteristics evaluation result are shown in following table 1.
2 > of < comparative example
Other than replacing copper foil to use the stainless steel foil of same thickness as negative electrode collector, in the same manner as comparative example 1 Sulfide solid battery is made, self discharge inspection and cycle characteristics evaluation are carried out.By the specification of battery, self discharge inspection result and Cycle characteristics evaluation result is shown in following table 1.
1 > of < reference example
In addition to replacing copper foil to use the stainless steel foil of same thickness for similarly to Example 1 as negative electrode collector Sulfide solid battery is made, self discharge inspection and cycle characteristics evaluation are carried out.By the specification of battery, self discharge inspection result and Cycle characteristics evaluation result is shown in following table 1.
It is found that by making comprising pre-doping material in cathode agent, self discharge amount is substantially reduced result as shown in Table 1. Reduce the cathode potential at the initial stage of sulfide solid battery by pre-doping material, it is suppressed that copper foil and sulfide solid are electrolysed The reaction of matter.The amount of pre-doping material contained by cathode agent is not particularly limited, though in cathode agent it is micro containing Pre-doping material can also play certain effect, but according to Examples 1 to 8 it is found that in the pre-doping material that cathode agent includes The ratio between the total capacity (Y) of silicon-based active material that the capacity conversion value (X) and cathode agent of the total amount of the lithium of doping include (X/Y) Preferably 0.0005 or more.In the case that especially X/Y is 0.0008 or more, self discharge amount is suppressed to 0.18V or so, puts certainly Electric inhibitory effect reaches saturation.Alternatively, according to Examples 1 to 8 it is found that negative electrode active material and the total of pre-doping material are set For 100 mass %, negative electrode active material is preferably set as 70 mass % more than and less than 100 mass %, pre-doping material is set For greater than 0 mass % and 30 mass % or less.In the case where considering capacity of negative plates etc., such as negative electrode active material is more preferably 90 Quality % or more, further preferably 93 mass % or more, particularly preferably 96 mass % or more, pre-doping material is more preferably 10 mass % hereinafter, further preferably 7 mass % hereinafter, particularly preferably 4 mass % or less.
In addition, according to Examples 1 to 8 and the result of comparative example 1 it is found that using the case where copper foil is as negative electrode collector Under, by making comprising pre-doping material in cathode agent, the cycle characteristics of sulfide solid battery is improved.
In addition, according to the result of embodiment 6 and 7 it is found that even if mixing in the type for changing negative electrode active material and/or in advance In the case where the type of miscellaneous material, same effect can be also obtained.
Furthermore as shown in comparative example 2 and reference example 1, pass through the metal material of negative electrode collector being changed to other than copper (stainless steel etc.), also can be avoided the generation of CuS, make the reduction of self discharge amount.But in this case, battery other than self discharge Each reduced performance.Such as the cycle characteristics of battery shown in comparative example 2 reduces.Furthermore according to the result of comparative example 2 and reference example 1 It is found that, even if in cathode agent including pre-doping material, circulation is special in the case where using stainless steel foil as negative electrode collector Property is also difficult to improve.This is because stainless steel foil is than copper foil hard, it is difficult to follow the expansion of negative electrode active material when charge and discharge It shrinks.
As can be observed from the foregoing, on the surface of negative electrode collector, setting includes silicon-based active material and sulfide solid electrolyte Anode mixture layer in the case where, compared with using generation of the negative electrode collector made of the material other than copper to avoid CuS, Using cupric negative electrode collector and make preferably inhibit CuS's comprising scheduled pre-doping material in cathode agent It generates.
Industry utilizability
The sulfide solid battery manufactured using the manufacturing method of the disclosure, such as it can be used in portable equipment use extensively Miniature Power Unit so that vehicle loading large-scale power supply.

Claims (3)

1. a kind of manufacturing method of sulfide solid battery, has following process:
1st process, selected from graphite and lithium titanate at least one of elements doped lithium in material, obtain pre-doping material；
Sulfide solid electrolyte, silicon-based active material and the pre-doping material are mixed, obtain cathode agent by the 2nd process； And
3rd process is laminated the cathode agent on the surface of the negative electrode collector of cupric, obtains cathode.
2. the manufacturing method of sulfide solid battery according to claim 1,
The capacity conversion value X of the total amount of the lithium adulterated in the pre-doping material for making the cathode agent include, it is born with described The ratio between the total capacity Y of the silicon-based active material that pole mixture includes X/Y becomes 0.0005 or more.
3. the manufacturing method of sulfide solid battery according to claim 1 or 2,
In the 1st process, using the electrochemical reaction in lithium ion battery, elements doped lithium in the material.
CN201811186908.0A 2017-12-08 2018-10-12 Method for manufacturing sulfide solid-state battery Active CN109904523B (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2017236384 2017-12-08
JP2017-236384 2017-12-08
JP2018087219A JP6996414B2 (en) 2017-12-08 2018-04-27 Manufacturing method of sulfide solid-state battery
JP2018-087219 2018-04-27

Publications (2)

Publication Number Publication Date
CN109904523A true CN109904523A (en) 2019-06-18
CN109904523B CN109904523B (en) 2022-03-15

Family

ID=67061430

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811186908.0A Active CN109904523B (en) 2017-12-08 2018-10-12 Method for manufacturing sulfide solid-state battery

Country Status (5)

Country Link
JP (1) JP6996414B2 (en)
KR (1) KR102165762B1 (en)
CN (1) CN109904523B (en)
BR (1) BR102018074749A2 (en)
RU (1) RU2695127C1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114613940A (en) * 2020-12-03 2022-06-10 丰田自动车株式会社 All-solid-state battery

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111908437A (en) * 2020-08-21 2020-11-10 中南大学 Preparation method of sulfide solid electrolyte
CN113972379B (en) * 2021-11-02 2023-01-10 北京科技大学 Method for preparing copper foil by using solid electrolyte and copper foil prepared by method
JP2023114598A (en) 2022-02-07 2023-08-18 トヨタ自動車株式会社 negative electrode layer
CN115995600B (en) * 2023-03-22 2023-08-15 中国科学院宁波材料技术与工程研究所 Element doped sulfide solid electrolyte with coating layer and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5595837A (en) * 1995-04-12 1997-01-21 Valence Technology, Inc. Process for prelithiation of carbon based anodes for lithium batteries
US20150037688A1 (en) * 2013-07-31 2015-02-05 Ngk Insulators, Ltd. All-Solid-State Cell
US20150171428A1 (en) * 2013-12-13 2015-06-18 Samsung Electronics Co., Ltd. All solid secondary battery and method of preparing all solid secondary battery
JP2015115194A (en) * 2013-12-11 2015-06-22 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． All-solid-state secondary battery and method for manufacturing all-solid-state secondary battery
CN105027346A (en) * 2013-03-26 2015-11-04 古河电气工业株式会社 All-solid-state secondary battery
CN106505203A (en) * 2015-09-08 2017-03-15 丰田自动车株式会社 Sulfide solid battery
US20170244097A1 (en) * 2016-02-18 2017-08-24 Toyota Jidosha Kabushiki Kaisha Cathode mixture, cathode, and all-solid-state lithium ion secondary battery, and method for manufacturing the same
US20170301910A1 (en) * 2014-09-29 2017-10-19 A123 Systems Llc Pre-lithiated silicon anodes with pvdf binder

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007227328A (en) * 2006-01-24 2007-09-06 Sanyo Electric Co Ltd Negative electrode for lithium secondary battery, method of manufacturing the electrode, and lithium secondary battery
JP5659696B2 (en) * 2009-12-24 2015-01-28 ソニー株式会社 Lithium ion secondary battery, negative electrode for lithium ion secondary battery, electric tool, electric vehicle and power storage system
JP6246816B2 (en) * 2013-09-02 2017-12-13 三菱瓦斯化学株式会社 All solid battery
JP6278385B2 (en) * 2013-11-02 2018-02-14 国立研究開発法人産業技術総合研究所 Non-aqueous secondary battery pre-doping method and battery obtained by the pre-doping method
JP6666641B2 (en) * 2013-12-13 2020-03-18 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． All-solid secondary battery and method for manufacturing all-solid secondary battery
JP2017037748A (en) * 2015-08-07 2017-02-16 日立化成株式会社 Negative electrode for lithium ion secondary battery and lithium ion secondary battery using the same
JP6497282B2 (en) * 2015-09-10 2019-04-10 トヨタ自動車株式会社 Negative electrode for all-solid-state battery

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5595837A (en) * 1995-04-12 1997-01-21 Valence Technology, Inc. Process for prelithiation of carbon based anodes for lithium batteries
CN105027346A (en) * 2013-03-26 2015-11-04 古河电气工业株式会社 All-solid-state secondary battery
US20150037688A1 (en) * 2013-07-31 2015-02-05 Ngk Insulators, Ltd. All-Solid-State Cell
JP2015115194A (en) * 2013-12-11 2015-06-22 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． All-solid-state secondary battery and method for manufacturing all-solid-state secondary battery
US20150171428A1 (en) * 2013-12-13 2015-06-18 Samsung Electronics Co., Ltd. All solid secondary battery and method of preparing all solid secondary battery
US20170301910A1 (en) * 2014-09-29 2017-10-19 A123 Systems Llc Pre-lithiated silicon anodes with pvdf binder
CN106505203A (en) * 2015-09-08 2017-03-15 丰田自动车株式会社 Sulfide solid battery
US20170244097A1 (en) * 2016-02-18 2017-08-24 Toyota Jidosha Kabushiki Kaisha Cathode mixture, cathode, and all-solid-state lithium ion secondary battery, and method for manufacturing the same
CN107093764A (en) * 2016-02-18 2017-08-25 丰田自动车株式会社 Anode mixture, positive pole and all-solid-state lithium-ion secondary battery and their manufacture method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114613940A (en) * 2020-12-03 2022-06-10 丰田自动车株式会社 All-solid-state battery
CN114613940B (en) * 2020-12-03 2023-08-04 丰田自动车株式会社 All-solid battery

Also Published As

Publication number Publication date
BR102018074749A2 (en) 2019-06-25
JP2019106352A (en) 2019-06-27
JP6996414B2 (en) 2022-01-17
RU2695127C1 (en) 2019-07-22
KR102165762B1 (en) 2020-10-14
KR20190068435A (en) 2019-06-18
CN109904523B (en) 2022-03-15

Similar Documents

Publication Publication Date Title
CN109904523A (en) The manufacturing method of sulfide solid battery
Wilhelm et al. Significant electrochemical performance improvement of TiSnSb as anode material for Li-ion batteries with composite electrode formulation and the use of VC and FEC electrolyte additives
KR101752566B1 (en) Active material composite particles and lithium battery
CN108844878A (en) Negative pole piece, method for testing active specific surface area of pole piece and battery
CN105580169A (en) Positive electrode active substance layer
CN101295788A (en) Active material, electrode, battery, and method of manufacturing active material
TW201801378A (en) Battery paste, battery electrode plate, and preparation method therefor
EP3496188B1 (en) Method for producing sulfide solid-state battery
CN108808068A (en) Secondary battery
US10998540B2 (en) Method for producing sulfide solid-state battery, and sulfide solid-state battery
CN109273760A (en) A kind of lithium ion cell electrode piece and coating method with solid-state electrolyte layer
KR20150027026A (en) Electrode for lithium ion secondary cell, method for preparing paste for said electrode and method for manufacturing said electrode
CN109428126A (en) Aqueous electrolyte and aquo-lithium ion secondary cell
CN109428048B (en) Method for producing negative electrode for aqueous lithium ion secondary battery and method for producing aqueous lithium ion secondary battery
WO2014205186A2 (en) Electrochemical device electrode including cobalt oxyhydroxide
CN109509921A (en) Aquo-lithium ion secondary cell
JP6662353B2 (en) Negative electrode current collector, negative electrode, and aqueous lithium ion secondary battery
Pu et al. Trapping polysulfides catholyte in carbon nanofiber sponges for improving the performances of sulfur batteries
Apraksin et al. Impedance of LiFe 0.4 Mn 0.6 PO 4 electrodes with combined conducting polymer binder of PEDOT: PSS and carboxymethyl cellulose
US20220115691A1 (en) Method for producing all solid-state battery, and all solid-state battery
JP2018181816A (en) Lithium ion secondary battery
Zhang et al. Effects of polyacrylic acid on the suppression of Fe deposition on graphite for lithium-ion batteries
TW200830606A (en) Electrolyte for lithium ion batteries
JP2017111989A (en) Electrode for all-solid battery, all-solid battery, and manufacturing methods thereof
EP4345953A1 (en) Positive electrode mixture layer, electroconductive auxiliary agent, positive electrode mixture, and lithium ion secondary battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant