CN111799466A - Flexible solid-state battery containing electron conduction interface layer and preparation method thereof - Google Patents

Flexible solid-state battery containing electron conduction interface layer and preparation method thereof Download PDF

Info

Publication number
CN111799466A
CN111799466A CN202010602287.0A CN202010602287A CN111799466A CN 111799466 A CN111799466 A CN 111799466A CN 202010602287 A CN202010602287 A CN 202010602287A CN 111799466 A CN111799466 A CN 111799466A
Authority
CN
China
Prior art keywords
lithium
layer
polymer electrolyte
bis
interface layer
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.)
Pending
Application number
CN202010602287.0A
Other languages
Chinese (zh)
Inventor
盛欧微
金成滨
陈媚
郑家乐
居治金
张文魁
陶新永
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.)
Zhejiang University of Technology ZJUT
Original Assignee
Zhejiang University of Technology ZJUT
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 Zhejiang University of Technology ZJUT filed Critical Zhejiang University of Technology ZJUT
Priority to CN202010602287.0A priority Critical patent/CN111799466A/en
Publication of CN111799466A publication Critical patent/CN111799466A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • 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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • 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

Abstract

The invention discloses a flexible solid-state battery containing an electron conduction interface layer and a preparation method thereof. The flexible solid battery comprises a positive electrode layer, a flexible polymer electrolyte layer, a metal lithium negative electrode layer and an electronic conduction interface layer, wherein the electronic conduction interface layer is positioned between the metal lithium negative electrode layer and the flexible polymer electrolyte layer, the electronic conduction interface layer is made of at least one of gold, silver, zinc, magnesium, aluminum, platinum, silicon, tin and selenium, and the thickness of the electronic conduction interface layer is 1-15 nm. The invention solves the problem of interface instability of the solid polymer electrolyte and the metallic lithium cathode, effectively prevents the short circuit of the battery and prolongs the cycle life of the battery.

Description

Flexible solid-state battery containing electron conduction interface layer and preparation method thereof
(I) technical field
The invention belongs to the technical field of solid-state lithium batteries, and relates to a flexible solid-state battery and a preparation method thereof.
(II) background of the invention
The solid electrolyte can replace the traditional flammable and explosive organic electrolyte to construct a safe lithium battery due to the solid nature of the solid electrolyte. Furthermore, the solid electrolyte has great potential to be matched with a lithium metal negative electrode to form an all solid lithium metal battery, wherein the lithium metal negative electrode has extremely high energy density of 3861mAh g-1And the lowest reduction potential (-3.04V). The next generation of all-solid-state lithium metal battery has high energy density, is safe and has great application prospect. However, the design of the interface of the lithium metal negative electrode and the polymer electrolyte is still a key issue that hinders the practical development of all-solid batteries. Due to the high reducibility of lithium metal, most polymer electrolytes react with lithium metal to undergo bond scission, especially polymers containing carbonate or ester groups. For example, when the polymer polyethylene oxide contacts lithium bistrifluoromethanesulfonylimide with lithium, lithium is immediately oxidized to lithium oxide by active oxygen groups in the polymer electrolyte, resulting in the aggregation of lithium ions and bistrifluoromethanesulfonylimide anions at the interface, slowing down the kinetics of ion transport, while polyethylene oxide decomposes to ethylene and hydrogen. In addition, vacancies are formed on the lithium surface during the electrochemical process, and the interface contact between lithium and an electrolyte is poor due to the increase of the vacancies on the lithium surface because the self-diffusion speed of lithium atoms for filling the vacancies is slow. Both aspects reduce the cycle life of the half and full cells. Therefore, how to reduce the persistent side reactions of lithium and polymer electrolytes, reducing lithium surface vacancy generation is a great challenge for flexible solid-state battery applications.
Disclosure of the invention
The invention aims to provide a high-safety high-energy-density flexible solid-state battery and a preparation method thereof, so as to solve the problem of interface instability of a solid polymer electrolyte and a metal lithium cathode, effectively prevent short circuit of the battery and prolong the cycle life of the battery.
The following specifically describes the technical means of the present invention.
In a first aspect, the invention provides a flexible solid battery, which comprises a positive electrode layer, a flexible polymer electrolyte layer, a metal lithium negative electrode layer and an electron conduction interface layer, wherein the electron conduction interface layer is positioned between the metal lithium negative electrode layer and the flexible polymer electrolyte layer, the electron conduction interface layer is made of at least one of gold, silver, zinc, magnesium, aluminum, platinum, silicon, tin and selenium, and the thickness of the electron conduction interface layer is 1-15 nm.
In the invention, the electronic conduction interface layer is added, so that the charge distribution on the interface is more uniform, the local charge is reduced, and the uniform deposition of lithium is promoted; and the existence of the electronic conduction interface layer can prevent the continuous interface reaction of the polymer electrolyte and the metallic lithium, prevent the reductive decomposition of the polymer and reduce the generation of lithium surface vacancies.
Preferably, the material of the electron-conducting interface layer is platinum or gold, and most preferably platinum.
Preferably, the thickness of the electron-conducting interfacial layer is from 2 to 11nm, most preferably 5 nm.
The positive electrode layer and the flexible polymer electrolyte layer according to the present invention may be manufactured by a conventional method using a conventional design in the art.
Preferably, the positive electrode layer is prepared by the following method: coating a composite positive electrode consisting of an active substance, a conductive agent and a polymer electrolyte on an aluminum foil or a carbon-coated aluminum foil by a scraper, and drying to obtain a positive electrode layer, wherein the active substance is lithium iron phosphate, lithium cobaltate or ternary nickel cobalt manganese.
As a further preference, the polymer electrolyte is selected from the group consisting of polyethylene oxide-lithium bistrifluoromethylsulfonyl imide (PEO-LiTFSI), polyethylene oxide-lithium perchlorate (PEO-LiClO)4) Polyethylene oxide-lithium bis-fluorosulfonimide (PEO-LiFSI), polyoxyethylenebis (fluorosulfonyl imide)Ethylene bis (oxalato) lithium borate (PEO-LiBOB), polyethylene oxide bis (oxalato) lithium borate (PEO-LiDFOB), polyacrylonitrile bis (trifluoromethylsulfonyl) imide lithium (PAN-LiTFSI), polyacrylonitrile bis (fluorosulfonyl) imide lithium (PAN-LiFSI), polyacrylonitrile lithium perchlorate (PAN-LiClO)4) Polyacrylonitrile-lithium bis (oxalato) borate (PAN-LiBOB), and polyacrylonitrile-lithium (difluorooxalato) borate (PAN-lidob).
More preferably, the conductive agent is any one of acetylene black, ketjen black, carbon nanotubes, conductive graphite, graphene, and carbon fibers.
As a further optimization, the feeding mass percentage of the active material, the conductive agent and the polymer electrolyte is 75-85%: 5-10%: 10 to 15 percent.
Preferably, the flexible polymer electrolyte layer is formed by depositing a polymer electrolyte on the positive electrode layer, wherein the polymer electrolyte is selected from the group consisting of polyethylene oxide-bis (trifluoromethyl) sulfonimide lithium (PEO-LiTFSI), and polyethylene oxide-lithium perchlorate (PEO-LiClO)4) Polyethylene oxide-lithium bis (fluorosulfonyl) imide (PEO-LiFSI), polyethylene oxide-lithium bis (oxalato) borate (PEO-LiBOB), polyethylene oxide-lithium bis (oxalato) borate (PEO-lidobo), polyacrylonitrile-lithium bis (trifluoromethylsulfonyl) imide (PAN-LiTFSI), polyacrylonitrile-lithium bis (fluorosulfonyl) imide (PAN-LiFSI), polyacrylonitrile-lithium perchlorate (PAN-LiClO)4) Polyacrylonitrile-lithium bis (oxalato) borate (PAN-LiBOB), and polyacrylonitrile-lithium (difluorooxalato) borate (PAN-lidob).
In a second aspect, the present invention provides a method for manufacturing a flexible solid-state battery, comprising the steps of:
(1) preparing a positive electrode layer;
(2) depositing a flexible polymer electrolyte layer on the positive electrode layer obtained in the step (1);
(3) depositing an electronic conduction interface layer on the flexible polymer electrolyte layer by an atomic layer deposition method, a magnetron sputtering method, pulse laser deposition or a 3D printing technology; the preparation of the electron conduction interface layer is carried out in the environment with the water content less than 10 ppm;
(4) placing a metal lithium strip on the electron conduction interface layer, and applying pressure to ensure that the metal lithium strip is well contacted with the interface layer;
(5) and assembling the flexible solid-state battery to control the thickness of the whole flexible solid-state battery to be 1-3 mm.
In step (1) of the present invention, the positive electrode layer is preferably prepared by the following method: coating a composite positive electrode consisting of an active substance, a conductive agent and a polymer electrolyte on an aluminum foil or a carbon-coated aluminum foil by a scraper, and drying to obtain a positive electrode layer, wherein the active substance is lithium iron phosphate, lithium cobaltate or ternary nickel cobalt manganese.
As a further preference, the polymer electrolyte in step (1) is selected from the group consisting of polyethylene oxide-bis (trifluoromethyl) sulfonyl imide lithium (PEO-LiTFSI), polyethylene oxide-lithium perchlorate (PEO-LiClO)4) Polyethylene oxide-lithium bis (fluorosulfonyl) imide (PEO-LiFSI), polyethylene oxide-lithium bis (oxalato) borate (PEO-LiBOB), polyethylene oxide-lithium bis (oxalato) borate (PEO-lidobo), polyacrylonitrile-lithium bis (trifluoromethylsulfonyl) imide (PAN-LiTFSI), polyacrylonitrile-lithium bis (fluorosulfonyl) imide (PAN-LiFSI), polyacrylonitrile-lithium perchlorate (PAN-LiClO)4) Polyacrylonitrile-lithium bis (oxalato) borate (PAN-LiBOB), and polyacrylonitrile-lithium (difluorooxalato) borate (PAN-lidob).
More preferably, the conductive agent is any one of acetylene black, ketjen black, carbon nanotubes, conductive graphite, graphene, and carbon fibers.
As a further optimization, the feeding mass percentage of the active material, the conductive agent and the polymer electrolyte is 75-85%: 5-10%: 10 to 15 percent.
In step (2) of the present invention, it is preferable to deposit a flexible polymer electrolyte layer on the positive electrode layer obtained in step (1) by: and obtaining a polymer electrolyte solution, coating the polymer electrolyte solution on the positive electrode layer by using a scraper, and volatilizing the solvent to obtain the flexible polymer electrolyte layer. The solvent of the polymer electrolyte solution may be determined according to the specific selected polymer electrolyte, and is preferably a solvent having good solubility for the polymer electrolyte and easy volatilization.
In step (4) of the present invention, a pressure of 5 to 15MPa is preferably applied, and a pressure of 8MPa is more preferably applied, so as to ensure that the contact between the lithium metal strip and the interface layer is good.
The high-safety high-energy-density flexible battery provided by the invention can be used in wearable electronic equipment with high capacity and long service life.
Compared with the prior art, the invention has the beneficial effects that:
the electron conduction interface layer can be used as a central site for lithium deposition or form an alloy in the charge-discharge process, so that the uniform deposition of lithium is promoted, and the interface is stabilized;
the electronic conduction interface layer provided by the invention can accelerate interface conduction, prevent bond breaking of carbon-oxygen bonds, stabilize polymer electrolyte and prolong cycle life in the charging and discharging processes;
the electron conduction interface layer provided by the invention can enable a formed solid electrolyte interface film (SEI) to be more stable in the charging and discharging processes, protect a lithium cathode and a polymer electrolyte and prolong the service life of a flexible battery;
the electronic conduction interface layer provided by the invention can keep stable circulation of the flexible battery under higher current density due to the improvement of the interface;
the volume and the weight of the flexible solid-state battery are simplified, the process is simple, and the flexible solid-state battery is suitable for large-scale production.
(IV) description of the drawings
Fig. 1 is a graph showing lithium-lithium cycle performance of solid polymer electrolytes with and without a platinum electron-conducting modification layer prepared in comparative example 1 and example 1 according to the present invention.
Fig. 2 is a graph showing the resistance curves of lithium batteries with and without the platinum electron conduction modification layer according to comparative example 1 and example 1 of the present invention after different cycles, (a) without the electron conduction modification layer, and (b) with the platinum electron conduction modification layer.
Fig. 3 is an Atomic Force Microscope (AFM) image of the surface of the electrolyte after 100 cycles of lithium batteries with and without platinum electron conduction modification layers according to comparative example 1 and example 1 of the present invention, (a) no electron conduction modification layer, (b) platinum electron conduction modification layer.
Fig. 4 is a cross-sectional view of the electrolyte surface after 100 cycles of the lithium batteries with and without the platinum electron conduction modification layer according to comparative example 1 and example 1 of the present invention, (a) without the electron conduction modification layer, and (b) with the platinum electron conduction modification layer.
Fig. 5 is a graph of the lithium-lithium cycling performance of solid polymer electrolytes with different thicknesses of platinum electron-conducting modification layers prepared in examples 1 and 2 of the present invention.
Fig. 6 is a graph of the lithium-lithium cycling performance of solid polymer electrolytes for different electron-conducting modification layers (platinum or gold) prepared in examples 1 and 5 of the present invention.
(V) detailed description of the preferred embodiment
The technical solution of the present invention is further described below by using specific examples, but the scope of the present invention is not limited thereto.
Example 1
0.375g LiFePO was weighed out separately40.05g of super-P and 0.075g of PEO-LiTFSI electrolyte, stirring and uniformly mixing by a slurry machine, coating the mixture on a carbon-coated aluminum foil with the length of 4 multiplied by 5cm by a scraper, and drying the mixture for 24 hours at the temperature of 60 ℃ for later use. Then 0.44g of PEO and 0.1435g of LiTFSI were dissolved in 10mL of anhydrous acetonitrile, stirred for 24h, coated on the positive electrode layer with a doctor blade, placed in a drying room with a dew point of-60 ℃ to volatilize for 3h at room temperature, and volatilized for 12h at 50 ℃ to remove the solvent, thereby forming a polymer electrolyte layer. Then, in a drying room with a dew point of-60 ℃, a magnetron sputtering instrument is adopted to deposit a 5nm metal platinum layer on the polymer layer as an electronic conduction interface layer by controlling sputtering current and sputtering time. On the electron-conducting interface layer, a metallic lithium ribbon was placed, and a pressure of 8MPa was applied to ensure good contact at the interface (observed by scanning the cross-section). And finally, sealing by using an aluminum plastic film, welding a tab and assembling a 3-layer flexible soft-package battery with the thickness of 2 mm.
Comparative example 1
A comparative flexible all-solid-state battery was obtained by assembling a flexible all-solid-state battery according to the positive electrode, the polymer electrolyte and the negative electrode without the electron-conductive interface layer-metal platinum layer, and otherwise the same as in example 1.
To test the effect of the electron-conducting interfacial layer-platinum layer stabilizing interface, 0.1mA cm was applied at 50 deg.C-2At current density of 0.1mAh cm-2The charge and discharge test was performed at capacity. As shown in fig. 1, the modification of the platinum layerThe cycle life of the lithium-lithium half cell is over 2000h by decoration (Pt-5 electrolyte), the cycle life of the lithium-lithium half cell is only 350h without the decoration (Pt-0 electrolyte) of a platinum layer, the cell is short-circuited after 350h, and the function of stabilizing the interface of the platinum layer can be seen. Fig. 2 traces the impedance change during the electrochemical cycling of the lithium battery, when no electron-conducting interface layer is modified, the interface impedance decreases from 380 Ω to 360 Ω after 100 cycles (216 hours) of cycling, then the interface impedance decreases sharply with the increase of cycling, and after 200 cycles (433 hours), the interface impedance is only 45 Ω, which indicates that the interface deteriorates sharply and the all-solid-state battery is short-circuited. And the use of the electronic conduction interface layer-metal platinum layer can see that the interface impedance of the battery after 0,100,200 and 300 circles is 470,440,380 and 230 omega respectively, the impedance is gradually reduced along with the increase of the cycle, but the phenomenon of sharp reduction does not exist, and the platinum layer has the beneficial effects of effectively preventing the short circuit of the battery and prolonging the cycle life of the battery. The flexible solid-state battery after 100 cycles was disassembled and the electrolyte surface (side near the lithium metal) was observed with AFM, and in fig. 3, the roughness of the Pt-0 electrolyte surface was about 53nm, and the uneven surface was also visible to the naked eye, whereas the roughness of the Pt-5 electrolyte surface was only 24nm, much lower than that of the Pt-0 electrolyte, corresponding to the post-cycle SEM observation of fig. 4, which also demonstrates the advantage of the presence of the electron-conducting interfacial layer.
Example 2
A flexible pouch cell was prepared following the procedure of example 1 except that the thickness of the electron-conducting interfacial layer-the metallic platinum layer was changed to 2nm, 8nm and 11 nm.
In order to test the effect of the stable interface of the electron conduction interface layer-metal platinum layer with different thicknesses, the temperature is 50 ℃, and the thickness is 0.1mAcm-2At current density of 0.1mAh cm-2The charge and discharge test was performed at capacity. As shown in FIG. 5, the cycle life of the lithium-lithium half cell is 1200, 2000, 1600 and 1300h respectively due to the modification of different platinum layers (Pt-2, Pt-5, Pt-8 and Pt-11 electrolytes), which is obviously improved compared with the modification without platinum layers (Pt-0 electrolyte), and the effect of stabilizing the interface of the platinum layers is seen. Similarly, it is stated that the thickness of the electron-conducting interfacial layer has a great influence on the cycle life, with increasing thickness, the poles of the lithium-lithium half-cellThe conversion increases and the cycle life of the half cell decreases when the thickness is more than 5 nm.
Example 3
0.375g LiCoO was weighed out separately20.05g Keqin black, 0.075g PAN-LiClO4And (3) stirring and uniformly mixing the electrolyte and the slurry by using a machine, coating the mixture on a carbon-coated aluminum foil with the thickness of 4 multiplied by 5cm by using a scraper, and drying the mixture for 24 hours at the temperature of 80 ℃ for later use. Then 0.44g PAN and 0.08g LiClO were mixed4Dissolving in 10mL of dimethylformamide solution, stirring for 24h, coating on the positive electrode layer by using a scraper, placing in a drying room with a dew point of-60 ℃, volatilizing at 80 ℃ for 24h, and removing the solvent to form a polymer electrolyte layer. Then, in a drying room with dew point of-60 ℃, 5nm of metal silver layer is deposited on the polymer layer as an electronic conduction interface layer by adopting atomic layer deposition and controlling time. And placing a metal lithium band on the electron conduction interface layer, and applying 8MPa pressure to ensure the contact of the interface. And finally, sealing by using an aluminum plastic film, welding a tab and assembling a 3-layer flexible soft-package battery with the thickness of 2 mm.
Comparative example 2
Without the electron-conducting interface layer-metallic silver layer, a flexible all-solid-state battery was assembled from the positive electrode, polymer electrolyte, and negative electrode, otherwise as in example 3, to obtain a comparative flexible all-solid-state battery.
In order to test the effect of the electron-conducting interfacial layer-metallic silver layer stable interface, 0.1mA cm was applied at 50 deg.C-2At current density of 0.1mAh cm-2The charge and discharge test was performed at capacity. The result proves that the metallic silver modified layer has the function of stabilizing the interface.
Example 4
0.425g of ternary nickel-cobalt-manganese, 0.025g of conductive carbon black and 0.05g of PAN-LiTFSI electrolyte are respectively weighed, stirred and uniformly mixed by a slurry machine, coated on a carbon-coated aluminum foil with the thickness of 4 multiplied by 5cm by a scraper, and dried for 24 hours at the temperature of 80 ℃ for standby. Then 0.44g PAN and 0.1435g LiTFSI were dissolved in 10mL dimethylformamide solution, stirred for 24h, coated on the positive electrode layer with a doctor blade, placed in a drying room with dew point-60 ℃ and evaporated at 80 ℃ for 24h to remove the solvent, and a polymer electrolyte layer was formed. Then, in a drying room with dew point of-60 ℃, 5nm of metallic tin layer is deposited on the polymer layer as an electronic conduction interface layer by adopting atomic layer deposition and controlling time. And placing a metal lithium band on the electron conduction interface layer, and applying 8MPa pressure to ensure the contact of the interface. And finally, sealing by using an aluminum plastic film, welding a tab and assembling 5 layers of flexible soft-package batteries, wherein the thickness is 3 mm.
Comparative example 3
Without the electron-conducting interface layer-metallic tin layer, a flexible all-solid battery was assembled from the positive electrode, polymer electrolyte, and negative electrode, otherwise as in example 4, to obtain a comparative flexible all-solid battery.
To test the effect of the electron-conducting interfacial layer-metallic tin layer stable interface, 0.1mA cm was applied at 50 deg.C-2At current density of 0.1mAh cm-2The charge and discharge test was performed at capacity. The results prove that the metallic tin modification layer has the function of stabilizing the interface.
Example 5
0.425g of LiFePO were weighed out separately40.025g of super-P and 0.05g of PEO-LiTFSI electrolyte, stirring and uniformly mixing by a slurry machine, coating on a carbon-coated aluminum foil with the length of 4 x 5cm by a scraper, and drying for 24 hours at the temperature of 60 ℃ for later use. Then 0.44g of PEO and 0.1435g of LiTFSI were dissolved in 10mL of anhydrous acetonitrile solution, stirred for 24h, coated on the positive electrode layer with a doctor blade, placed in a drying room with a dew point of-60 ℃ to volatilize for 3h at room temperature, and volatilized for 12h at 50 ℃ to remove the solvent, thereby forming a polymer electrolyte layer. And depositing a metal gold layer with the thickness of 5nm on the polymer layer as an electronic conduction interface layer by adopting a magnetron sputtering instrument and controlling the sputtering current and the sputtering time in a drying room with the dew point of-60 ℃. And placing a metal lithium band on the electron conduction interface layer, and applying 8MPa pressure to ensure the contact of the interface. And finally, sealing by using an aluminum plastic film, and welding a tab to assemble the flexible soft package battery with the thickness of 2 mm.
To test the effect of the electron-conducting interface layer-gold metal layer stable interface, 0.1mA cm was applied at 50 deg.C-2At current density of 0.1mAh cm-2The charge and discharge test was performed at capacity. It is seen from the comparative data in fig. 6 that the deposition of the gold layer can improve the cycle life of the lithium battery, but the effect of the platinum layer (example 1) is more obvious, the service life of the battery is longer (2000h), and the polarization voltage of the interface modified by the platinum layer is smaller than that of the interface modified by the gold layer.

Claims (10)

1. A flexible solid-state battery comprising a positive electrode layer, a flexible polymer electrolyte layer, and a metallic lithium negative electrode layer, characterized in that: the flexible solid battery also comprises an electronic conduction interface layer, wherein the electronic conduction interface layer is positioned between the metal lithium negative electrode layer and the flexible polymer electrolyte layer, the electronic conduction interface layer is made of at least one of gold, silver, zinc, magnesium, aluminum, platinum, silicon, tin and selenium, and the thickness of the electronic conduction interface layer is 1-15 nm.
2. The flexible solid-state battery according to claim 1, wherein: the material of the electron conduction interface layer is platinum or gold.
3. The flexible solid-state battery according to claim 1, wherein: the material of the electron conduction interface layer is platinum.
4. The flexible solid-state battery according to any one of claims 1 to 3, wherein: the thickness of the electronic conduction interface layer is 2-11 nm.
5. The flexible solid-state battery according to claim 4, wherein: the thickness of the electron conduction interface layer is 5 nm.
6. A method of making a flexible solid-state battery of claim 1, comprising the steps of:
(1) preparing a positive electrode layer;
(2) depositing a flexible polymer electrolyte layer on the positive electrode layer obtained in the step (1);
(3) depositing an electronic conduction interface layer on the flexible polymer electrolyte layer by an atomic layer deposition method, a magnetron sputtering method, pulse laser deposition or a 3D printing technology; the preparation of the electron conduction interface layer is carried out in the environment with the water content less than 10 ppm;
(4) placing a metal lithium strip on the electron conduction interface layer, and applying pressure to ensure that the metal lithium strip is well contacted with the interface layer;
(5) and assembling the flexible solid-state battery to control the thickness of the whole flexible solid-state battery to be 1-3 mm.
7. The method of claim 6, wherein: in the step (1), the positive electrode layer is prepared by the following method: coating a composite positive electrode consisting of an active substance, a conductive agent and a polymer electrolyte on an aluminum foil or a carbon-coated aluminum foil by a scraper, and drying to obtain a positive electrode layer, wherein the active substance is lithium iron phosphate, lithium cobaltate or ternary nickel cobalt manganese.
8. The method of claim 7, wherein: the polymer electrolyte in the step (1) is selected from any one of polyoxyethylene-lithium imide, polyoxyethylene-lithium perchlorate, polyoxyethylene-bis (fluorosulfonyl) bis (trifluoromethanesulfonimide) lithium, polyoxyethylene-bis (oxalato) lithium borate, polyacrylonitrile-bis (trifluoromethanesulfonyl) lithium, polyacrylonitrile-bis (fluorosulfonato) lithium, polyacrylonitrile-lithium perchlorate, polyacrylonitrile-bis (oxalato) lithium borate and polyacrylonitrile-bis (oxalato) lithium borate;
the conductive agent is any one of acetylene black, Ketjen black, carbon nanotubes, conductive graphite, graphene and carbon fibers;
the mass percentages of the active substance, the conductive agent and the polymer electrolyte are 75-85%: 5-10%: 10 to 15 percent.
9. The method of claim 6, wherein: in the step (2), a flexible polymer electrolyte layer is deposited on the positive electrode layer obtained in the step (1) by: obtaining a polymer electrolyte solution, coating the polymer electrolyte solution on the positive electrode layer by using a scraper, and volatilizing the solvent to obtain a flexible polymer electrolyte layer; the polymer electrolyte is selected from any one of polyethylene oxide-lithium imide, polyethylene oxide-lithium perchlorate, polyethylene oxide-bis (fluorosulfonyl) bis (trifluoromethyl) sulfonimide lithium, polyethylene oxide-bis (oxalato) lithium borate, polyacrylonitrile-bis (trifluoromethyl) sulfonimide lithium, polyacrylonitrile-bis (fluorosulfonato) imide lithium, polyacrylonitrile-lithium perchlorate, polyacrylonitrile-bis (oxalato) lithium borate and polyacrylonitrile-bis (oxalato) lithium borate.
10. The method of claim 6, wherein: in the step (4), 5-15MPa pressure is applied to ensure that the metal lithium belt and the interface layer are well contacted.
CN202010602287.0A 2020-06-28 2020-06-28 Flexible solid-state battery containing electron conduction interface layer and preparation method thereof Pending CN111799466A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010602287.0A CN111799466A (en) 2020-06-28 2020-06-28 Flexible solid-state battery containing electron conduction interface layer and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010602287.0A CN111799466A (en) 2020-06-28 2020-06-28 Flexible solid-state battery containing electron conduction interface layer and preparation method thereof

Publications (1)

Publication Number Publication Date
CN111799466A true CN111799466A (en) 2020-10-20

Family

ID=72804756

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010602287.0A Pending CN111799466A (en) 2020-06-28 2020-06-28 Flexible solid-state battery containing electron conduction interface layer and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111799466A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112687960A (en) * 2020-12-28 2021-04-20 浙江省科创新材料研究院 Method for stabilizing solid electrolyte/metal negative electrode interface by using zinc salt
CN114242942A (en) * 2021-11-30 2022-03-25 厦门大学 Composite buffer layer with stable negative electrode interface and solid-state lithium metal battery thereof
CN114551782A (en) * 2021-08-16 2022-05-27 万向一二三股份公司 Lithium metal negative electrode coated with protective layer and preparation method and application thereof
CN116404247A (en) * 2023-06-09 2023-07-07 西北工业大学 PE-based polymer solid electrolyte and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1415122A (en) * 1999-11-23 2003-04-30 分子技术股份有限公司 Lithium anodes for electrochemical cells
CN1601791A (en) * 2004-10-21 2005-03-30 复旦大学 Full solid film lithium cell and its prepn process
CN110518278A (en) * 2019-08-19 2019-11-29 南方科技大学 Solid electrolyte and preparation method and solid state battery with cathode interface layer
US20190393486A1 (en) * 2018-06-21 2019-12-26 Nanotek Instruments, Inc. Method of improving anode stability in a lithium metal secondary battery
CN111293353A (en) * 2018-12-06 2020-06-16 大众汽车有限公司 Protective layer for lithium metal anode of solid state battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1415122A (en) * 1999-11-23 2003-04-30 分子技术股份有限公司 Lithium anodes for electrochemical cells
CN1601791A (en) * 2004-10-21 2005-03-30 复旦大学 Full solid film lithium cell and its prepn process
US20190393486A1 (en) * 2018-06-21 2019-12-26 Nanotek Instruments, Inc. Method of improving anode stability in a lithium metal secondary battery
CN111293353A (en) * 2018-12-06 2020-06-16 大众汽车有限公司 Protective layer for lithium metal anode of solid state battery
CN110518278A (en) * 2019-08-19 2019-11-29 南方科技大学 Solid electrolyte and preparation method and solid state battery with cathode interface layer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
OUWEI SHENG等: "Platinum nano-interlayer enhanced interface for stable all-solid-state batteries observed via cryotransmission electron microscopy", 《JOURNAL OF MATERIALS CHEMISTRY A》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112687960A (en) * 2020-12-28 2021-04-20 浙江省科创新材料研究院 Method for stabilizing solid electrolyte/metal negative electrode interface by using zinc salt
CN114551782A (en) * 2021-08-16 2022-05-27 万向一二三股份公司 Lithium metal negative electrode coated with protective layer and preparation method and application thereof
CN114551782B (en) * 2021-08-16 2023-07-07 万向一二三股份公司 Lithium metal negative electrode coated with protective layer and preparation method and application thereof
CN114242942A (en) * 2021-11-30 2022-03-25 厦门大学 Composite buffer layer with stable negative electrode interface and solid-state lithium metal battery thereof
CN116404247A (en) * 2023-06-09 2023-07-07 西北工业大学 PE-based polymer solid electrolyte and preparation method and application thereof

Similar Documents

Publication Publication Date Title
Tian et al. Recently advances and perspectives of anode-free rechargeable batteries
Wu et al. Perspectives for restraining harsh lithium dendrite growth: Towards robust lithium metal anodes
US11374254B2 (en) Solid state electrolyte for lithium secondary battery
US10680287B2 (en) Hybrid solid state electrolyte for lithium sulfur secondary battery
Peng et al. Alloy‐type anodes for high‐performance rechargeable batteries
CN111063863B (en) Metal lithium composite negative electrode material and preparation method and application thereof
CN111799466A (en) Flexible solid-state battery containing electron conduction interface layer and preparation method thereof
KR100324623B1 (en) Carbon electrodes coated with porous metal film, its fabrication method and lithium secondary battery using it
CN111900485B (en) Slow-release modification method for solid electrolyte/metal lithium interface and solid lithium metal battery
CN110476283B (en) Protective layer for metal electrode battery
Li et al. P4S10 modified lithium anode for enhanced performance of lithium–sulfur batteries
CN113299871B (en) Lithium battery cathode and method for preparing same by adopting solid electrochemical corrosion method
Ren et al. A safe and efficient lithiated silicon-sulfur battery enabled by a bi-functional composite interlayer
CN112928238A (en) Ultrathin metal lithium electrode, preparation thereof and application of ultrathin metal lithium electrode as negative electrode of secondary lithium battery
Gu et al. Toward high-performance Li metal anode via difunctional protecting layer
Wei et al. Interfacial engineering on metal anodes in rechargeable batteries
Bhujbal et al. Recent Advances in Prelithiation of Si Anode: Enhanced Strategy for Boosting Practicability of Li-Ion Battery
CN115440987A (en) Current collector and preparation method thereof, negative electrode and electrochemical energy storage device
Hu et al. Graphene film with folds for a stable lithium metal anode
CN110800136B (en) Positive electrode for lithium-sulfur battery and lithium-sulfur battery comprising same
Tan et al. A Li3Bi/LiF interfacial layer enabling highly stable lithium metal anode
Zheng et al. In situ construction of inorganic component-rich polymers as interfacial stabilizers for high-rate lithium metal batteries
CN115810720A (en) Composite anode for lithium secondary battery and method for manufacturing the same
Kang et al. A stable protective layer toward high-performance lithium metal battery
CN113206219A (en) 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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20201020