CN107706352A - A kind of anode pole piece applied to flexible solid lithium battery and preparation method thereof - Google Patents

A kind of anode pole piece applied to flexible solid lithium battery and preparation method thereof Download PDF

Info

Publication number
CN107706352A
CN107706352A CN201710953205.5A CN201710953205A CN107706352A CN 107706352 A CN107706352 A CN 107706352A CN 201710953205 A CN201710953205 A CN 201710953205A CN 107706352 A CN107706352 A CN 107706352A
Authority
CN
China
Prior art keywords
pole piece
anode pole
lithium battery
flexible solid
solid lithium
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
CN201710953205.5A
Other languages
Chinese (zh)
Other versions
CN107706352B (en
Inventor
冯玉川
李峥
何泓材
何朝凌
杨帆
南策文
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.)
Qingtao Kunshan Energy Development Co ltd
Original Assignee
Qing Tao (kunshan) Energy Developments Ltd
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 Qing Tao (kunshan) Energy Developments Ltd filed Critical Qing Tao (kunshan) Energy Developments Ltd
Priority to CN201710953205.5A priority Critical patent/CN107706352B/en
Publication of CN107706352A publication Critical patent/CN107706352A/en
Application granted granted Critical
Publication of CN107706352B publication Critical patent/CN107706352B/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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—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
    • H01M4/1391—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
    • H01M4/1397—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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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

Abstract

The invention discloses a kind of anode pole piece applied to flexible solid lithium battery of the invention, it is characterised in that：This anode pole piece is made up of following material, including：Active material, fast-ionic conductor, conductive agent, film forming agent, lithium salts and solvent, prepared the invention also discloses slurry, coating is toasted, prepared by collector, is preserved.What the present invention was reached has the technical effect that：Prepared pole piece according to the method described above, can self-supporting film forming have it is flexible well, fast-ionic conductor and the lithium salts of film forming agent mixing are dispersed in pole piece simultaneously, it can be good at providing lithium ion tunnel, pole piece is set just to have good ionic conducting property in the case where not needing electrolyte, therefore this pole piece is suitably applied in solid lithium ion battery.

Description

A kind of anode pole piece applied to flexible solid lithium battery and preparation method thereof
Technical field
The present invention relates to new energy lithium electrical domain, is related to a kind of anode pole piece applied to flexible solid lithium battery, especially It is related to a kind of preparation method of the anode pole piece applied to flexible solid lithium battery.
Background technology
Intelligent terminal continues to develop in recent years, and the speed of update is more and more faster, the flexibility of device and equipment The target that always product development personnel and consumer pursue jointly, it is near in Flexible Displays and flexible wearable apparatus field No small technological progress is achieved over year, but fails really to realize flexibility always with the flexible battery of flexible apparatus, This is very big to limit the exploitation of flexible product.Chargeable, energy density is high, long lifespan etc. because it has for lithium rechargeable battery Advantage and be widely used, but flexible lithium rechargeable battery is not still come out without successful product development.One of them is most Chief reason is exactly that there is presently no prepare bending, turning round with anode pole piece flexible very well, traditional anode pole piece Active material easily peels off from collector during song, and this results in battery, performance drastically declines after bending, distortion, very Safety problem can extremely be produced.
Solid lithium ion battery replaces being electrolysed compared to traditional liquid lithium ionic cell as a result of solid electrolyte Liquid, safer, energy density is higher, simultaneously because solid electrolyte can be with the extraordinary polymer film of pliability, because And with can flexibility the characteristics of.At present solid flexible battery be typically utilized on flexible parent metal plate successively positive electrode, It is prepared by the mode of electrolyte and this plated film of negative material, although the battery being prepared with certain flexibility, Capacity is small, and high expensive.Want to prepare Large Copacity, the flexible solid battery of low cost, the preparation of flexible pole piece is to close Key.
The content of the invention
The purpose of the present invention is：For above-mentioned deficiency, there is provided a kind of anode pole piece applied to flexible solid lithium battery and Its preparation method.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：
A kind of anode pole piece applied to flexible solid lithium battery, this anode pole piece are made up of following material, including：Activity Material, fast-ionic conductor, conductive agent, film forming agent, lithium salts and solvent.
The active material is cobalt acid lithium, LiFePO 4, one kind in tertiary cathode material, and its quality accounting is 80%-95%.
The fast-ionic conductor is lithium lanthanum zirconium oxygen, lithium lanthanum zirconium tantalum oxygen, Li-La-Ti oxygen, mix the Li-La-Ti oxygen of aluminium etc. it is inorganic soon from One kind in sub- conductor material, diameter of particle are 0.3 micron~1 micron, and quality accounting is 1%-5%.
The conductive agent is acetylene black, carbon fiber, CNT, graphene one or several kinds of mixture therein, Quality accounting is 1%-5%.
The film forming agent is polyethylene glycol oxide, Kynoar, one kind or two of which in polymethyl methacrylate Mixture in proportion, quality accounting are 1%-10%.
The lithium salts is Li-TFSI, LiClO4, LiPF6, and one kind in LiBO4, LiAsF6, quality accounting is 1%- 8%.
The solvent is 1-METHYLPYRROLIDONE solvent, by active material wherein in solvent, fast-ionic conductor, and conductive agent, The solid material accounting of film forming agent composition is 30%-50%.
A kind of preparation method of anode pole piece applied to flexible solid lithium battery, it is characterised in that：
Step 1: prepared by slurry：Film forming agent is added in solvent, is stirred dissolving, after its dissolving, is added conductive Agent, it is stirred after disperseing, adds fast-ionic conductor and continue scattered stirring, active material is added after being uniformly dispersed, then It is sufficiently stirred, is afterwards added obtained slurry in remaining solvent, the mass ratio for adjusting its solids content is 30%- 50%, viscosity 10000, it is eventually adding lithium salts and is stirred；
Step 2: coating baking：The slurry prepared is coated, applies cloth base material selection mould release membrance, coating environment control Humidity dew point processed is below -20 °, and then by baking film forming, baking is divided into 80 DEG C of bakings, 110 DEG C of bakings, and 130 DEG C are toasted, and 80 DEG C four-stage is toasted, and baking time is respectively 1min, 3min, 5min and 3min；
Step 3: prepared by collector：Pole piece after drying is separated with mould release membrance, the pole piece film after separation utilizes steaming The method of plating plates last layer collector in the one side of membrane material, and thickness is 100 nanometers；
Step 4: preserve：The pole piece prepared is subjected to vacuum sealing preservation, waited standby.
The mould release membrance is PET mould release membrances, the aluminium foil after surface treatment, one kind in copper foil after surface treatment.
The collector can be one kind in platinum, gold and aluminium.
Compared with prior art, what the present invention was reached has the technical effect that：Prepared pole piece according to the method described above, can be certainly Film forming is supported, there is flexibility well, while fast-ionic conductor and the lithium salts of film forming agent mixing are dispersed in pole piece, energy It is enough that lithium ion tunnel is provided well, pole piece is just had good ionic conducting property in the case where not needing electrolyte, because This this pole piece is suitably applied in solid lithium ion battery.
Brief description of the drawings
Fig. 1 is the charging and discharging curve for the 0.1C for preparing flexible solid lithium battery.
Embodiment
Below in conjunction with the accompanying drawings and embodiment the invention will be further described：
Embodiment one：
A kind of anode pole piece applied to flexible solid lithium battery of the invention, this anode pole piece are made up of following material, wrap Include：Active material, fast-ionic conductor, conductive agent, film forming agent, lithium salts and solvent.
The active material is LiFePO 4, and its quality accounting is 80%.
The fast-ionic conductor is lithium lanthanum zirconium oxygen, and diameter of particle is 0.3 micron, and quality accounting is 5%.
The conductive agent is carbon fiber, and quality accounting is 5%.
The film forming agent is polyethylene glycol oxide, and quality accounting is 5.
The lithium salts is LiClO4, and quality accounting is 5.
The solvent is 1-METHYLPYRROLIDONE solvent, by LiFePO 4 wherein in solvent, lithium lanthanum zirconium oxygen, and carbon fiber, The solid material accounting of polyethylene glycol oxide composition is 30%.
A kind of preparation method of anode pole piece applied to flexible solid lithium battery, it is characterised in that：Step 1: slurry system It is standby：Polyethylene glycol oxide is added in 1-METHYLPYRROLIDONE solvent, is stirred dissolving, after its dissolving, adds carbon fiber, It is stirred after disperseing, adds lithium lanthanum zirconium oxygen and continue scattered stirring, active material is added after being uniformly dispersed, then filled Divide stirring, obtained slurry is added in remaining 1-METHYLPYRROLIDONE solvent afterwards, adjusts the quality of its solids content Than for 30%, viscosity 10000, being eventually adding LiClO4 and being stirred；
Step 2: coating baking：The slurry prepared is coated, applies cloth base material selection mould release membrance, coating environment control Humidity dew point processed is below -20 °, and then by baking film forming, baking is divided into 80 DEG C of bakings, 110 DEG C of bakings, and 130 DEG C are toasted, and 80 DEG C four-stage is toasted, and baking time is respectively 1min, 3min, 5min and 3min；
Step 3: prepared by collector：Pole piece after drying is separated with mould release membrance, the pole piece film after separation utilizes steaming The method of plating plates last layer collector in the one side of membrane material, and thickness is 100 nanometers；
Step 4: preserve：The pole piece prepared is subjected to vacuum sealing preservation, waited standby.
The mould release membrance is PET mould release membrances.
The collector is platinum.
Embodiment two：
A kind of anode pole piece applied to flexible solid lithium battery of the invention, this anode pole piece are made up of following material, wrap Include：Active material, fast-ionic conductor, conductive agent, film forming agent, lithium salts and solvent.
The active material is tertiary cathode material, and its quality accounting is 83%.
The fast-ionic conductor is lithium lanthanum zirconium tantalum oxygen, and diameter of particle is 0.4 micron, and quality accounting is 1%.
The conductive agent is CNT, and quality accounting is 1%.
The film forming agent is Kynoar, and quality accounting is 10%.
The lithium salts is LiPF6, and quality accounting is 5%.
The solvent is 1-METHYLPYRROLIDONE solvent, by active material wherein in solvent, fast-ionic conductor, and conductive agent, The solid material accounting of film forming agent composition is 40%.
A kind of preparation method of anode pole piece applied to flexible solid lithium battery, it is characterised in that：Step 1: slurry system It is standby：Kynoar is added in 1-METHYLPYRROLIDONE solvent, is stirred dissolving, after its dissolving, adds carbon nanometer Pipe, it is stirred after disperseing, adds lithium lanthanum zirconium tantalum oxygen and continue scattered stirring, tertiary cathode material is added after being uniformly dispersed Material, then be sufficiently stirred, obtained slurry is added in remaining 1-METHYLPYRROLIDONE solvent afterwards, adjusts its solid The mass ratio of content is 40%, viscosity 10000, is eventually adding LiPF6 and is stirred；
Step 2: coating baking：The slurry prepared is coated, applies cloth base material selection mould release membrance, coating environment control Humidity dew point processed is below -20 °, and then by baking film forming, baking is divided into 80 DEG C of bakings, 110 DEG C of bakings, and 130 DEG C are toasted, and 80 DEG C four-stage is toasted, and baking time is respectively 1min, 3min, 5min and 3min；
Step 3: prepared by collector：Pole piece after drying is separated with mould release membrance, the pole piece film after separation utilizes steaming The method of plating plates last layer collector in the one side of membrane material, and thickness is 100 nanometers；
Step 4: preserve：The pole piece prepared is subjected to vacuum sealing preservation, waited standby.
The mould release membrance is the aluminium foil after surface treatment.
The collector is gold.
Embodiment three：
A kind of anode pole piece applied to flexible solid lithium battery of the invention, this anode pole piece are made up of following material, wrap Include：Active material, fast-ionic conductor, conductive agent, film forming agent, lithium salts and solvent.
The active material is LiFePO 4, and its quality accounting is 85%.
The fast-ionic conductor is the Li-La-Ti oxygen for mixing aluminium, and diameter of particle is 0.6 micron, and quality accounting is 3%.
The conductive agent is graphene, and quality accounting is 3%.
The film forming agent is polymethyl methacrylate, and quality accounting is 1%.
The lithium salts is LiBO4, and quality accounting is 8%.
The solvent is 1-METHYLPYRROLIDONE solvent, by active material wherein in solvent, fast-ionic conductor, and conductive agent, The solid material accounting of film forming agent composition is 45%.
A kind of preparation method of anode pole piece applied to flexible solid lithium battery, it is characterised in that：Step 1: slurry system It is standby：Polymethyl methacrylate is added in 1-METHYLPYRROLIDONE solvent, is stirred dissolving, after its dissolving, is added Graphene, it is stirred after disperseing, the Li-La-Ti oxygen that aluminium is mixed in addition continues scattered stirring, and phosphoric acid is added after being uniformly dispersed Ferrous lithium, then be sufficiently stirred, obtained slurry is added in remaining 1-METHYLPYRROLIDONE solvent afterwards, adjusts it The mass ratio of solids content is 45%, viscosity 10000, is eventually adding lithium salts and is stirred；
Step 2: coating baking：The slurry prepared is coated, applies cloth base material selection mould release membrance, coating environment control Humidity dew point processed is below -20 °, and then by baking film forming, baking is divided into 80 DEG C of bakings, 110 DEG C of bakings, and 130 DEG C are toasted, and 80 DEG C four-stage is toasted, and baking time is respectively 1min, 3min, 5min and 3min；
Step 3: prepared by collector：Pole piece after drying is separated with mould release membrance, the pole piece film after separation utilizes steaming The method of plating plates last layer collector in the one side of membrane material, and thickness is 100 nanometers；
Step 4: preserve：The pole piece prepared is subjected to vacuum sealing preservation, waited standby.
The mould release membrance is PET mould release membrances.
The collector can be aluminium.
Example IV：
A kind of anode pole piece applied to flexible solid lithium battery of the invention, this anode pole piece are made up of following material, wrap Include：Active material, fast-ionic conductor, conductive agent, film forming agent, lithium salts and solvent.
The active material is cobalt acid lithium, and its quality accounting is 90%.
The fast-ionic conductor is Li-La-Ti oxygen, and diameter of particle is 0.8 micron, and quality accounting is 2%.
The conductive agent is acetylene black, and quality accounting is 2%.
The film forming agent is the mixture in Kynoar and polymethyl methacrylate, and quality accounting is 3%.
The lithium salts is Li-TFSI, and quality accounting is 3%.
The solvent is 1-METHYLPYRROLIDONE solvent, by active material wherein in solvent, fast-ionic conductor, and conductive agent, The solid material accounting of film forming agent composition is 34%.
A kind of preparation method of anode pole piece applied to flexible solid lithium battery, it is characterised in that：Step 1: slurry system It is standby：Mixture in Kynoar and polymethyl methacrylate is added in 1-METHYLPYRROLIDONE solvent, stirred Dissolving is mixed, after its dissolving, acetylene black is added, is stirred after disperseing, Li-La-Ti oxygen is added and continues scattered stirring, disperse Cobalt acid lithium is added after uniformly, then is sufficiently stirred, obtained slurry is added into remaining 1-METHYLPYRROLIDONE afterwards In solvent, the mass ratio for adjusting its solids content is 34%, viscosity 10000, is eventually adding lithium salts and is stirred；
Step 2: coating baking：The slurry prepared is coated, applies cloth base material selection mould release membrance, coating environment control Humidity dew point processed is below -20 °, and then by baking film forming, baking is divided into 80 DEG C of bakings, 110 DEG C of bakings, and 130 DEG C are toasted, and 80 DEG C four-stage is toasted, and baking time is respectively 1min, 3min, 5min and 3min；
Step 3: prepared by collector：Pole piece after drying is separated with mould release membrance, the pole piece film after separation utilizes steaming The method of plating plates last layer collector in the one side of membrane material, and thickness is 100 nanometers；
Step 4: preserve：The pole piece prepared is subjected to vacuum sealing preservation, waited standby.
The mould release membrance is PET mould release membrances, the aluminium foil after surface treatment, one kind in copper foil after surface treatment.
The collector can be one kind in platinum, gold and aluminium.
Embodiment five：
A kind of anode pole piece applied to flexible solid lithium battery of the invention, this anode pole piece are made up of following material, wrap Include：Active material, fast-ionic conductor, conductive agent, film forming agent, lithium salts and solvent.
The active material is LiFePO 4, and its quality accounting is 95%.
The fast-ionic conductor is lithium lanthanum zirconium oxygen, and diameter of particle is 1 micron, and quality accounting is 1%
The conductive agent is the mixture of carbon fiber and CNT, and quality accounting is 1%.
The film forming agent is polyethylene glycol oxide, and the mixture of polymethyl methacrylate, quality accounting is 2%.
The lithium salts is LiAsF6, and quality accounting is 1%.
The solvent is 1-METHYLPYRROLIDONE solvent, by active material wherein in solvent, fast-ionic conductor, and conductive agent, The solid material accounting of film forming agent composition is 50%.
A kind of preparation method of anode pole piece applied to flexible solid lithium battery, it is characterised in that：Step 1: slurry system It is standby：By polyethylene glycol oxide, the mixture of polymethyl methacrylate is added in 1-METHYLPYRROLIDONE solvent, is stirred molten Solution, after its dissolving, add the mixture of carbon fiber and CNT, be stirred it is scattered after, add lithium lanthanum zirconium oxygen continue into The scattered stirring of row, adds LiFePO 4 after being uniformly dispersed, then is sufficiently stirred, and afterwards adds obtained slurry surplus In remaining 1-METHYLPYRROLIDONE solvent, the mass ratio for adjusting its solids content is 50%, viscosity 10000, is eventually adding LiAsF6 is stirred；
Step 2: coating baking：The slurry prepared is coated, applies cloth base material selection mould release membrance, coating environment control Humidity dew point processed is below -20 °, and then by baking film forming, baking is divided into 80 DEG C of bakings, 110 DEG C of bakings, and 130 DEG C are toasted, and 80 DEG C four-stage is toasted, and baking time is respectively 1min, 3min, 5min and 3min；
Step 3: prepared by collector：Pole piece after drying is separated with mould release membrance, the pole piece film after separation utilizes steaming The method of plating plates last layer collector in the one side of membrane material, and thickness is 100 nanometers；
Step 4: preserve：The pole piece prepared is subjected to vacuum sealing preservation, waited standby.
The mould release membrance is PET mould release membrances.
The collector is platinum.
Embodiment six：
As shown in figure 1, the flexible positive plate prepared, the polymer dielectric film of solid-state, metal lithium sheet chi is cut out into It is very little after carry out lamination assembling, then it is packaged using flexible encapsulant material, by packaged battery 0.1C multiplying power Under tested, reach design capacity, by 500 times bending (radius of curvature 4cm) after, capability retention 97%.
Compared with prior art, what the present invention was reached has the technical effect that：Prepared pole piece according to the method described above, can be certainly Film forming is supported, there is flexibility well, while fast-ionic conductor and the lithium salts of film forming agent mixing are dispersed in pole piece, energy It is enough that lithium ion tunnel is provided well, pole piece is just had good ionic conducting property in the case where not needing electrolyte, because This this pole piece is suitably applied in solid lithium ion battery.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention The equivalent change or modification that Spirit Essence is made, it should all be included within the scope of the present invention.

Claims (10)

  1. A kind of 1. anode pole piece applied to flexible solid lithium battery, it is characterised in that：This anode pole piece is made up of following material, Including：Active material, fast-ionic conductor, conductive agent, film forming agent, lithium salts and solvent.
  2. A kind of 2. anode pole piece applied to flexible solid lithium battery according to claim 1, it is characterised in that：The work Property material is cobalt acid lithium, LiFePO 4, and one kind in tertiary cathode material, its quality accounting is 80%-95%.
  3. A kind of 3. anode pole piece applied to flexible solid lithium battery according to claim 1, it is characterised in that：It is described fast Ion conductor is lithium lanthanum zirconium oxygen, lithium lanthanum zirconium tantalum oxygen, Li-La-Ti oxygen, mixes one kind in the Li-La-Ti oxygen of aluminium, and diameter of particle is 0.3 micro- Rice~1 micron, quality accounting is 1%-5%.
  4. A kind of 4. anode pole piece applied to flexible solid lithium battery according to claim 1, it is characterised in that：It is described to lead Electric agent is acetylene black, and carbon fiber, CNT, graphene one or several kinds of mixture therein, quality accounting is 1%- 5%.
  5. A kind of 5. anode pole piece applied to flexible solid lithium battery according to claim 1, it is characterised in that：It is described into Film is polyethylene glycol oxide, Kynoar, the mixture of one kind or two of which in polymethyl methacrylate in proportion, Quality accounting is 1%-10%.
  6. A kind of 6. anode pole piece applied to flexible solid lithium battery according to claim 1, it is characterised in that：The lithium Salt is Li-TFSI, LiClO4, LiPF6, and one kind in LiBO4, LiAsF6, quality accounting is 1%-8%.
  7. 7. according to a kind of any one described anode pole piece applied to flexible solid lithium battery, its feature in claim 1 to 6 It is：The solvent is 1-METHYLPYRROLIDONE solvent, wherein by active material, fast-ionic conductor, conductive agent, film forming in solvent The solid material accounting of agent composition is 30%-50%.
  8. A kind of 8. preparation method of anode pole piece applied to flexible solid lithium battery, it is characterised in that：
    Step 1: prepared by slurry：Film forming agent is added in solvent, is stirred dissolving, after its dissolving, adds conductive agent, It is stirred after disperseing, adds fast-ionic conductor and continue scattered stirring, active material is added after being uniformly dispersed, then carry out It is sufficiently stirred, afterwards adds obtained slurry in remaining solvent, the mass ratio for adjusting its solids content is 30%- 50%, viscosity 10000, it is eventually adding lithium salts and is stirred；
    Step 2: coating baking：The slurry prepared is coated, applies cloth base material selection mould release membrance, coating environment control is wet Dew point is spent below -20 °, then by baking film forming, is toasted and is divided into 80 DEG C of bakings, 110 DEG C of bakings, 130 DEG C of bakings, 80 DEG C four The individual stage is toasted, and baking time is respectively 1min, 3min, 5min and 3min；
    Step 3: prepared by collector：Pole piece after drying is separated with mould release membrance, the pole piece film after separation utilizes evaporation Method plates last layer collector in the one side of membrane material, and thickness is 100 nanometers；
    Step 4: preserve：The pole piece prepared is subjected to vacuum sealing preservation, waited standby.
  9. 9. a kind of preparation method of anode pole piece applied to flexible solid lithium battery according to claim 8, its feature It is：The mould release membrance is PET mould release membrances, the aluminium foil after surface treatment, one kind in copper foil after surface treatment.
  10. 10. a kind of preparation method of anode pole piece applied to flexible solid lithium battery according to claim 8, its feature It is：The collector can be one kind in platinum, gold and aluminium.
CN201710953205.5A 2017-10-13 2017-10-13 Positive pole piece applied to flexible solid-state lithium battery and preparation method thereof Active CN107706352B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710953205.5A CN107706352B (en) 2017-10-13 2017-10-13 Positive pole piece applied to flexible solid-state lithium battery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710953205.5A CN107706352B (en) 2017-10-13 2017-10-13 Positive pole piece applied to flexible solid-state lithium battery and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107706352A true CN107706352A (en) 2018-02-16
CN107706352B CN107706352B (en) 2020-09-04

Family

ID=61185053

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710953205.5A Active CN107706352B (en) 2017-10-13 2017-10-13 Positive pole piece applied to flexible solid-state lithium battery and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107706352B (en)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108417777A (en) * 2018-04-28 2018-08-17 清陶（昆山）新能源材料研究院有限公司 A kind of porous triple anode composite piece and preparation method thereof and its application
CN108448169A (en) * 2018-03-15 2018-08-24 清陶（昆山）能源发展有限公司 A kind of inorganic-organic hybrid solid electrolyte membrane and its processing technology
CN108461711A (en) * 2018-03-21 2018-08-28 清陶（昆山）能源发展有限公司 A kind of nickel-cobalt-manganese ternary anode composite of room temperature solid flexible battery and preparation method thereof and application
CN108598368A (en) * 2018-06-28 2018-09-28 清陶（昆山）新能源材料研究院有限公司 A kind of all-solid lithium-ion battery composite negative pole and preparation method thereof
CN108598371A (en) * 2018-05-11 2018-09-28 清陶（昆山）新能源材料研究院有限公司 A kind of flexible solid lithium ion battery composite negative plate and preparation method thereof and the application in solid lithium ion battery
CN108808075A (en) * 2018-06-14 2018-11-13 东华大学 A kind of flexible inorganic solid electrolyte film and its preparation and application
CN108987754A (en) * 2018-07-25 2018-12-11 力信（江苏）能源科技有限责任公司 The preparation method of dispersing agent, the anode sizing agent containing dispersing agent and its lithium battery
CN109216705A (en) * 2018-09-17 2019-01-15 苏州清陶新能源科技有限公司 A kind of solid state battery conductive composite coating aluminium foil and its preparation process
CN109860595A (en) * 2018-12-26 2019-06-07 中国电子科技集团公司第十八研究所 A kind of solid state lithium battery compound binding agent and preparation method thereof
CN111211301A (en) * 2020-01-10 2020-05-29 上海工程技术大学 Flexible organic compound/biomass carbon fiber composite material and preparation method thereof
GB2580146A (en) * 2018-12-21 2020-07-15 Ilika Tech Limited Composite material
CN111697204A (en) * 2019-03-12 2020-09-22 杭州众达新能源材料有限公司 Lithium lanthanum zirconium oxide/lithium cobaltate composite material and preparation method and application thereof
CN111916747A (en) * 2020-08-11 2020-11-10 天津力神电池股份有限公司 High-safety polymer battery positive plate, polymer battery and battery preparation method
CN112086618A (en) * 2020-09-03 2020-12-15 星恒电源(滁州)有限公司 High-lithium-ion-conductivity positive plate and preparation method thereof
CN112086617A (en) * 2020-09-03 2020-12-15 星恒电源(滁州)有限公司 High-lithium-ion-conductivity positive plate and preparation method thereof
CN112786890A (en) * 2021-01-28 2021-05-11 合肥国轩高科动力能源有限公司 Solid-state battery with low interface impedance and preparation method thereof
CN112864353A (en) * 2021-04-01 2021-05-28 清华大学深圳国际研究生院 Positive electrode material, preparation method thereof, positive electrode and all-solid-state lithium ion battery
CN113471412A (en) * 2020-03-31 2021-10-01 北京卫蓝新能源科技有限公司 Composite conductive slurry, preparation method, positive pole piece and lithium ion battery
CN113764610A (en) * 2020-06-04 2021-12-07 恒大新能源技术(深圳)有限公司 Battery pole piece and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104485478A (en) * 2014-11-07 2015-04-01 东莞市鸿德电池有限公司 Flexible lithium ion battery and preparation method thereof
JP2016115415A (en) * 2014-12-11 2016-06-23 日揮触媒化成株式会社 Electrode material and solid oxide type fuel battery
CN105887016A (en) * 2016-05-24 2016-08-24 中国科学技术大学 Preparation method, product and application of flexible vanadium dioxide film
CN105932225A (en) * 2016-06-29 2016-09-07 中国科学院青岛生物能源与过程研究所 Preparation method of improved room temperature electron ion fast transfer electrode slice for solid-state secondary lithium battery
CN106159318A (en) * 2015-04-07 2016-11-23 中国科学院上海硅酸盐研究所 Novel slice type solid-state serondary lithium battery that garnet-type solid electrolyte supports and preparation method thereof
CN106299467A (en) * 2016-09-13 2017-01-04 清华大学 Composite solid electrolyte and flexible all-solid-state battery and preparation method, wearable electronic
CN106299237A (en) * 2016-09-27 2017-01-04 柔电（武汉）科技有限公司 Self-supporting pole piece and preparation method thereof, battery and battery core thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104485478A (en) * 2014-11-07 2015-04-01 东莞市鸿德电池有限公司 Flexible lithium ion battery and preparation method thereof
JP2016115415A (en) * 2014-12-11 2016-06-23 日揮触媒化成株式会社 Electrode material and solid oxide type fuel battery
CN106159318A (en) * 2015-04-07 2016-11-23 中国科学院上海硅酸盐研究所 Novel slice type solid-state serondary lithium battery that garnet-type solid electrolyte supports and preparation method thereof
CN105887016A (en) * 2016-05-24 2016-08-24 中国科学技术大学 Preparation method, product and application of flexible vanadium dioxide film
CN105932225A (en) * 2016-06-29 2016-09-07 中国科学院青岛生物能源与过程研究所 Preparation method of improved room temperature electron ion fast transfer electrode slice for solid-state secondary lithium battery
CN106299467A (en) * 2016-09-13 2017-01-04 清华大学 Composite solid electrolyte and flexible all-solid-state battery and preparation method, wearable electronic
CN106299237A (en) * 2016-09-27 2017-01-04 柔电（武汉）科技有限公司 Self-supporting pole piece and preparation method thereof, battery and battery core thereof

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108448169A (en) * 2018-03-15 2018-08-24 清陶（昆山）能源发展有限公司 A kind of inorganic-organic hybrid solid electrolyte membrane and its processing technology
CN108461711A (en) * 2018-03-21 2018-08-28 清陶（昆山）能源发展有限公司 A kind of nickel-cobalt-manganese ternary anode composite of room temperature solid flexible battery and preparation method thereof and application
CN108417777B (en) * 2018-04-28 2021-02-19 苏州清陶新能源科技有限公司 Porous ternary composite positive plate and preparation method and application thereof
CN108417777A (en) * 2018-04-28 2018-08-17 清陶（昆山）新能源材料研究院有限公司 A kind of porous triple anode composite piece and preparation method thereof and its application
CN108598371A (en) * 2018-05-11 2018-09-28 清陶（昆山）新能源材料研究院有限公司 A kind of flexible solid lithium ion battery composite negative plate and preparation method thereof and the application in solid lithium ion battery
CN108598371B (en) * 2018-05-11 2021-03-02 苏州清陶新能源科技有限公司 Composite negative plate for flexible solid-state lithium ion battery, preparation method of composite negative plate and application of composite negative plate in solid-state lithium ion battery
CN108808075B (en) * 2018-06-14 2020-06-23 东华大学 Flexible inorganic solid electrolyte film and preparation and application thereof
CN108808075A (en) * 2018-06-14 2018-11-13 东华大学 A kind of flexible inorganic solid electrolyte film and its preparation and application
CN108598368A (en) * 2018-06-28 2018-09-28 清陶（昆山）新能源材料研究院有限公司 A kind of all-solid lithium-ion battery composite negative pole and preparation method thereof
CN108987754A (en) * 2018-07-25 2018-12-11 力信（江苏）能源科技有限责任公司 The preparation method of dispersing agent, the anode sizing agent containing dispersing agent and its lithium battery
CN109216705A (en) * 2018-09-17 2019-01-15 苏州清陶新能源科技有限公司 A kind of solid state battery conductive composite coating aluminium foil and its preparation process
GB2580146B (en) * 2018-12-21 2023-05-24 Ilika Tech Limited Composite material
GB2580146A (en) * 2018-12-21 2020-07-15 Ilika Tech Limited Composite material
CN109860595A (en) * 2018-12-26 2019-06-07 中国电子科技集团公司第十八研究所 A kind of solid state lithium battery compound binding agent and preparation method thereof
CN109860595B (en) * 2018-12-26 2022-03-04 中国电子科技集团公司第十八研究所 Composite binder for solid lithium battery and preparation method thereof
CN111697204A (en) * 2019-03-12 2020-09-22 杭州众达新能源材料有限公司 Lithium lanthanum zirconium oxide/lithium cobaltate composite material and preparation method and application thereof
CN111211301A (en) * 2020-01-10 2020-05-29 上海工程技术大学 Flexible organic compound/biomass carbon fiber composite material and preparation method thereof
CN113471412A (en) * 2020-03-31 2021-10-01 北京卫蓝新能源科技有限公司 Composite conductive slurry, preparation method, positive pole piece and lithium ion battery
CN113764610A (en) * 2020-06-04 2021-12-07 恒大新能源技术(深圳)有限公司 Battery pole piece and preparation method and application thereof
CN113764610B (en) * 2020-06-04 2022-10-18 恒大新能源技术(深圳)有限公司 Battery pole piece and preparation method and application thereof
CN111916747A (en) * 2020-08-11 2020-11-10 天津力神电池股份有限公司 High-safety polymer battery positive plate, polymer battery and battery preparation method
CN111916747B (en) * 2020-08-11 2023-10-20 天津力神电池股份有限公司 High-safety polymer battery positive plate, polymer battery and battery preparation method
CN112086617A (en) * 2020-09-03 2020-12-15 星恒电源(滁州)有限公司 High-lithium-ion-conductivity positive plate and preparation method thereof
CN112086618A (en) * 2020-09-03 2020-12-15 星恒电源(滁州)有限公司 High-lithium-ion-conductivity positive plate and preparation method thereof
CN112786890A (en) * 2021-01-28 2021-05-11 合肥国轩高科动力能源有限公司 Solid-state battery with low interface impedance and preparation method thereof
CN112864353A (en) * 2021-04-01 2021-05-28 清华大学深圳国际研究生院 Positive electrode material, preparation method thereof, positive electrode and all-solid-state lithium ion battery

Also Published As

Publication number Publication date
CN107706352B (en) 2020-09-04

Similar Documents

Publication Publication Date Title
CN107706352A (en) A kind of anode pole piece applied to flexible solid lithium battery and preparation method thereof
CN103956458B (en) A kind of composite lithium ion battery anode and preparation method thereof and the application in all-solid-state battery
KR101655627B1 (en) Organic-inorganic complex solid polymer electrolytes membrane, manufacturing method thereof and all solid battery including thereof
Liu et al. Electrochemical performance of LiFePO4 cathode material coated with ZrO2 nanolayer
CN111009683B (en) Asymmetric semi-solid electrolyte, preparation method and metal lithium secondary battery
US20160118684A1 (en) Electrophoretic deposition of thin film batteries
CN108232156B (en) Silicon-carbon composite cathode for solid-state battery and preparation method thereof
CN107394255A (en) Composite electrolyte membrane and preparation method thereof and the solid lithium battery containing the film
CN108232111A (en) A kind of anode composite pole piece of solid state battery and preparation method thereof
CN108365258A (en) The solid electrolyte of polymer substrate and preparation method thereof with room-temperature conductivity
CN101626072A (en) Positive plate of lithium ion battery and preparation method thereof
CN108598371A (en) A kind of flexible solid lithium ion battery composite negative plate and preparation method thereof and the application in solid lithium ion battery
CN105932209A (en) Ceramic coating diaphragm for lithium ion battery and preparation method thereof
CN103474723A (en) Lithium-air battery and preparation method thereof
CN108365269A (en) A kind of coating processes of wet coating dielectric film coating machine
CN105428700A (en) Compound polymer electrolyte material, preparation method thereof, electrolyte membrane and all-solid-state lithium secondary battery
CN106941190A (en) The preparation method of garnet-type solid electrolyte material
CN112563567B (en) Composite solid electrolyte material, method for producing same, method for producing composite solid electrolyte membrane, and solid battery
CN107994257A (en) A kind of high-performance solid electrolyte and preparation method thereof
CN108428935A (en) A kind of solid electrolyte membrane preparation method and lithium battery
Hareendrakrishnakumar et al. Sulfonic groups stemmed ionic shield for polysulfides towards high performance Li–S batteries
CN108232120B (en) Synthesis of solid-state lithium battery and preparation method of graphite composite negative plate and lithium iron phosphate composite positive plate
Kum et al. Enhancing electrochemical performances of rechargeable lithium-ion batteries via cathode interfacial engineering
CN105098189B (en) Negative material additive and preparation method thereof
CN105870454A (en) Application method of graphene as conductive agent to positive electrode slurry of lithium ion 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
CP01 Change in the name or title of a patent holder
CP01 Change in the name or title of a patent holder

Address after: 2 / F, building 3, Dongchuang science and technology center, No.1 Hongfeng Road, enterprise science and Technology Park, East Qianjin Road, Kunshan Development Zone, Suzhou City, Jiangsu Province

Patentee after: Qingtao (Kunshan) Energy Development Co.,Ltd.

Address before: 2 / F, building 3, Dongchuang science and technology center, No.1 Hongfeng Road, enterprise science and Technology Park, East Qianjin Road, Kunshan Development Zone, Suzhou City, Jiangsu Province

Patentee before: QINGTAO (KUNSHAN) ENERGY DEVELOPMENT CO.,LTD.

CP02 Change in the address of a patent holder
CP02 Change in the address of a patent holder

Address after: Floor 2, Building 1, No. 3 Shengxi Road, Kunshan Development Zone, Suzhou City, Jiangsu Province, 215000

Patentee after: Qingtao (Kunshan) Energy Development Co.,Ltd.

Address before: 2 / F, building 3, Dongchuang science and technology center, No.1 Hongfeng Road, enterprise science and Technology Park, East Qianjin Road, Kunshan Development Zone, Suzhou City, Jiangsu Province

Patentee before: Qingtao (Kunshan) Energy Development Co.,Ltd.