CN110165286A - All-solid lithium-ion battery and its complex sintered preparation process of integration - Google Patents

All-solid lithium-ion battery and its complex sintered preparation process of integration Download PDF

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Publication number
CN110165286A
CN110165286A CN201910468555.1A CN201910468555A CN110165286A CN 110165286 A CN110165286 A CN 110165286A CN 201910468555 A CN201910468555 A CN 201910468555A CN 110165286 A CN110165286 A CN 110165286A
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electrolyte
electrode
anode
oxide
cathode
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高翔
黄逍逍
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Zhejiang Guoneng Lithium Industry Co Ltd
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Zhejiang Guoneng Lithium Industry Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • 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
    • 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

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

Abstract

The invention belongs to novel energy resource material technology fields, specially a kind of all-solid lithium-ion battery and its complex sintered preparation process of integration, all-solid lithium-ion battery includes that at least one electrode-electric solution matter compound electric pole piece is constituted, electrode is oxide lithium electricity anode or oxide cathode material in the electrode-electric solution matter compound electric pole piece, and electrolyte is solid oxide electrolysis matter.The present invention can effectively improve the interface problem of solid lithium battery, significantly improve the interface cohesion degree and interfacial structure stability between electrode and solid electrolyte, make single battery core has higher-density and energy density, it is provided simultaneously with very excellent security performance, is suitble to large-scale production and application.

Description

All-solid lithium-ion battery and its complex sintered preparation process of integration
Technical field
The invention belongs to novel energy resource material technology field, specially a kind of all-solid lithium-ion battery and its integration are compound It is sintered preparation process.
Background technique
Existing aqueous lithium ion battery, which uses, contains volatile, flammable organic solvent liquid or gel state electrolyte, The advantages of this kind of electrolyte be conductivity it is high but there are the shortcomings that it is also very much.Firstly, this kind of battery needs strict encapsulation, to protect Card liquid electrolyte does not leak, and the requirement of encapsulation brings the reduction of battery volume, and there are the limit；Secondly, liquid or gel state electrolysis Matter is mostly inflammable and explosive organic matter, and when heated, battery easily occurs to explode or burn, and this problem is to for onboard power Battery is more prominent.All-solid lithium-ion battery is electrolysed using non-volatile, non-combustible, stable structure solid-oxide lithium ion Matter, while because the relatively excellent mechanical strength of solid electrolyte is also provided with good puncture resistant ability (charge and discharge process Middle lithium branch crystals growth can cause internal short-circuit of battery through the liquid electrolyte of aqueous lithium battery easily).Therefore, all solid lithium Ion battery has very excellent safety and stability performance, it is considered to be the ideal of the dynamic lithium battery of next-generation large-scale use Selection.
In currently available technology, the preparation method of all-solid lithium-ion battery anode is generally divided into three kinds, i.e. pressed powder Type, Vacuum Deposition membranous type and application type.Pressed powder type be by positive electrode active materials, inorganic solid electrolyte powder and conductive agent by It mixes according to certain ratio, then suppresses under pressure, the electrode-electric solution material internal holes of this method preparation Gap rate is higher (being generally not less than 30%), and interfacial contact area is small between material granule, seriously affects the charge-discharge magnification of battery Energy and battery energy density；Vacuum Deposition membranous type is using evaporation coating, sputter coating, pulse laser deposition film or ion film plating etc. Mode directly by positive electrode active materials plated film on a current collector, this kind of method needs specific equipment, expensive, efficiency compared with It is low, commercial applications are constrained to a certain extent；Application type positive plate be by positive electrode active materials, inorganic solid electrolyte, Conductive agent and bonding agent are uniformly mixed in specific solvent according to a certain percentage, and mixed slurry is then coated in collection with ground On fluid, this kind of method is only capable of obtaining the lower electrode of consistency and electrolyte coating, leads to interfacial contact area between material granule Product charge-discharge magnification performance and battery energy density small and that seriously affect battery, while the adhesive component being added will affect The conduction of positive internal lithium ion, to influence the chemical property of battery.In order to solve the above-mentioned technical problem, the present invention discloses Integrated anode-electrolyte the laminar composite for preparing by high temperature sintering high-compactness, by greatly improving anode/electricity It solves matter/cathode interface to combine, significantly enhances solid lithium ion battery internal interface stability and interface transports performance and electricity The chemical property of pond entirety.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of all-solid lithium-ion battery and its integration are complex sintered Preparation process, including, at least one electrode-electric solution matter compound electric pole piece is constituted, electricity in the electrode-electric solution matter compound electric pole piece Extremely oxide lithium electricity anode or oxide cathode material, electrolyte are solid oxide electrolysis matter.
Preferably, the electrode-electric solution matter compound electric pole piece is positive pole with electrolyte integral type is complex sintered forms, or Negative electrode material and electrolyte integral type be complex sintered form or positive electrode, electrolyte, negative electrode material integral type it is complex sintered and At.
Preferably,
The positive electrode active materials are
LiCoO2、LiMnO2、LiNiO2、LiNixCoyMnzO2(x+y+z=1), LiMn2O4、LiNi0.5Mn1.5O4、 LiNixCoyAlzO2(x+y+z=1), LiMxNyNi0.5-yMn1.5-xO4(x+y+z=1, M, N=Fe, Ti, Co, Al), Li2MnO3In One or more (contain heterogeneous composite material),
Electrolyte is
Li3xLa0.67-xTiO3(0≤x≤0.17)、Li3xLa0.33-xNbO3(0≤x≤0.17)、Li7La3Zr2O12、 Li5La3M2O12One or more of (M=Ta, Nb),
Negative electrode material is Li4Ti5O12, metal Li, graphite, Si-C composite material, one of polymer cathode.
The complex sintered preparation process of integration, includes the following steps,
Step 1 prepares high pure oxide electrode (anode, cathode), oxide electrolyte powder；
Oxide electrode and oxide electrolyte powder are uniformly obtained seperated sample by step 2 through ball milling mixing respectively；
Step 3, the appropriate binder of addition, the content of the binder are 0-5%；
Conductive agent is added in step 4；
Step 5, pre-stamped standby sheet sample；
Step 6, by sheet sample according to anode/anode-electrolyte mixed phase/electrolyte/cathode or electrolyte/electrolysis Matter-cathode mixed phase/cathode or anode/anode-electrolyte mixed phase/electrolyte/electrolyte-cathode mixed phase/cathode sequence Superposition, is compacted through isostatic cool pressing.
Sample after step 7. will be compacted obtained by step 6 is placed in crucible or quartz ampoule, is placed into LiCO3 powder, carries out high Temperature sintering, obtains high compaction polarizing electrode-electrolyte composite sinter.
Compared with prior art, the present invention is achieved has the technical effect that through this technique, can effectively realize electrode- Electrolyte level densifies (> 90%) and granular boundary conjugation, realizes and significantly enhances boundary inside solid lithium ion battery Face stability and interface transport the chemical property of performance and battery entirety.Meanwhile the present invention designs solid lithium battery system Preparation Method is simple and efficient, and is easily manipulated, and preparation process is nearly free from any environmentally hazardous substance, environmentally protective, is suitble to big Technical scale production and application.
Other features and advantages of the present invention will be illustrated in the following description, also, partly becomes from specification It obtains it is clear that understand through the implementation of the invention.The objectives and other advantages of the invention can be by written explanation Specifically noted structure is achieved and obtained in book, claims and attached drawing.
Below by drawings and examples, technical scheme of the present invention will be described in further detail.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is using anode/electrolyte/cathode integration composite design all-solid lithium-ion battery；
Fig. 2 is using anode/electrolyte integration composite design all-solid lithium-ion battery.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
Embodiment one
As shown in Figure 1,
A kind of all-solid lithium-ion battery provided in this embodiment, including electrode-electric solution matter compound electric pole piece and metal electricity Pole, the metal electrode are set to the electrode-electric solution matter compound electric pole piece both ends, the electrode-electric solution matter compound electric pole piece By anode/anode-electrolyte mixed phase/electrolyte/electrolyte-cathode mixed phase/cathode laminated structure, it is compacted through isostatic cool pressing It forms, the negative electrode material is Li4Ti5O12, positive electrode LiNi0.8Co0.1Mn0.1O2, electrolyte Li0.33La0.56TiO3。
Embodiment two
As shown in Fig. 2,
A kind of all-solid lithium-ion battery provided in this embodiment, including electrode-electric solution matter compound electric pole piece and metal electricity Pole, the metal electrode are set to the electrode-electric solution matter compound electric pole piece both ends, the electrode-electric solution matter compound electric pole piece By anode/anode-electrolyte mixed phase/electrolyte/cathode laminated structure, it is compacted through isostatic cool pressing, the negative electrode material It is Si-C composite material, positive electrode LiNi in this implementation for non-oxidized substance0.8Co0.1Mn0.1O2, electrolyte is Li7La3Zr2O12。
Embodiment three
A kind of all-solid lithium-ion battery provided in this embodiment, including electrode-electric solution matter compound electric pole piece and metal electricity Pole, the metal electrode are set to the electrode-electric solution matter compound electric pole piece both ends, the electrode-electric solution matter compound electric pole piece By anode/anode-electrolyte mixed phase/electrolyte/electrolyte-cathode mixed phase/cathode laminated structure, it is compacted through isostatic cool pressing It forms, the negative electrode material is Li4Ti5O12, positive electrode LiNi0.8Co0.1Mn0.1O2, electrolyte Li7La3Zr2O12。
The unspecified content of the present invention, can be used the prior art, therefore do not repeating.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies Within, then the present invention is also intended to include these modifications and variations.

Claims (4)

1. all-solid lithium-ion battery, which is characterized in that it is constituted including at least one electrode-electric solution matter compound electric pole piece, it is described Electrode is oxide lithium electricity anode in electrode-electric solution matter compound electric pole piece or oxide cathode material, electrolyte are solid oxide Object electrolyte.
2. all-solid lithium-ion battery according to claim 1, which is characterized in that the electrode-electric solution matter combination electrode Piece be anode with electrolyte integral type it is complex sintered form or negative electrode material with electrolyte integral type is complex sintered forms, or just Pole material, electrolyte, negative electrode material integral type is complex sintered forms.
3. all-solid lithium-ion battery according to claim 1, which is characterized in that
The positive electrode active materials are
LiCoO2、LiMnO2、LiNiO2、LiNixCoyMnzO2(x+y+z=1), LiMn2O4、LiNi0.5Mn1.5O4、 LiNixCoyAlzO2(x+y+z=1), LiMxNyNi0.5-yMn1.5-xO4(x+y+z=1, M, N=Fe, Ti, Co, Al), Li2MnO3In One or more (contain heterogeneous composite material),
Electrolyte is
Li3xLa0.67-xTiO3(0≤x≤0.17)、Li3xLa0.33-xNbO3(0≤x≤0.17)、Li7La3Zr2O12、Li5La3M2O12 One or more of (M=Ta, Nb),
Negative electrode material is Li4Ti5O12, metal Li, graphite, Si-C composite material, one of polymer cathode.
4. the complex sintered preparation process of integration, which is characterized in that include the following steps,
Step 1 prepares high pure oxide electrode (anode, cathode), oxide electrolyte powder；
Oxide electrode and oxide electrolyte powder are uniformly obtained seperated sample by step 2 through ball milling mixing respectively；
Step 3, the appropriate binder of addition, the content of the binder are 0-5%；
Conductive agent is added in step 4；
Step 5, pre-stamped standby sheet sample；
Step 6 bears sheet sample according to anode/anode-electrolyte mixed phase/electrolyte/cathode or electrolyte/electrolyte- Pole mixed phase/cathode or anode/anode-electrolyte mixed phase/electrolyte/electrolyte-cathode mixed phase/cathode mixed phase are suitable Sequence superposition, is compacted through isostatic cool pressing；
Sample after step 7. will be compacted obtained by step 6 is placed in crucible or quartz ampoule, is placed into LiCO3 powder, carries out high temperature burning Knot obtains high compaction polarizing electrode-electrolyte composite sinter.
CN201910468555.1A 2019-05-31 2019-05-31 All-solid lithium-ion battery and its complex sintered preparation process of integration Withdrawn CN110165286A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111430789A (en) * 2019-11-29 2020-07-17 蜂巢能源科技有限公司 Method for reducing porosity of solid electrolyte layer and application thereof
CN111883855A (en) * 2020-08-31 2020-11-03 蜂巢能源科技有限公司 All-solid-state battery cell, preparation method thereof and solid-state battery
CN112054239A (en) * 2020-09-14 2020-12-08 昆山宝创新能源科技有限公司 Electrolyte and application thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111430789A (en) * 2019-11-29 2020-07-17 蜂巢能源科技有限公司 Method for reducing porosity of solid electrolyte layer and application thereof
CN111430789B (en) * 2019-11-29 2022-09-20 蜂巢能源科技有限公司 Method for reducing porosity of solid electrolyte layer and application thereof
CN111883855A (en) * 2020-08-31 2020-11-03 蜂巢能源科技有限公司 All-solid-state battery cell, preparation method thereof and solid-state battery
CN111883855B (en) * 2020-08-31 2021-08-27 蜂巢能源科技有限公司 All-solid-state battery cell, preparation method thereof and solid-state battery
CN112054239A (en) * 2020-09-14 2020-12-08 昆山宝创新能源科技有限公司 Electrolyte and application thereof

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