CN112310468A - Light-assisted enhanced secondary battery and preparation method thereof - Google Patents

Light-assisted enhanced secondary battery and preparation method thereof Download PDF

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Publication number
CN112310468A
CN112310468A CN201910701482.6A CN201910701482A CN112310468A CN 112310468 A CN112310468 A CN 112310468A CN 201910701482 A CN201910701482 A CN 201910701482A CN 112310468 A CN112310468 A CN 112310468A
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film
purity
moo
secondary battery
sputtering
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徐璟
耿浩
夏晖
卞海晨
孙硕
李晓舟
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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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
    • H01M10/05—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
    • H01M10/058—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)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a light-assisted enhanced secondary battery and a preparation method thereof. The light-assisted enhanced secondary battery is FTO conductive glass/MoO3/LiPON/Li/Cu, FTO conductive glass as substrate, MoO3The film is used as a positive electrode, the lithium phosphorus oxygen nitrogen film is used as a solid electrolyte film, the metal Li film is used as a negative electrode, and the metal Cu is used as a negative electrode current collector. According to the invention, the solid-state thin-film battery is prepared on the FTO conductive glass, so that the interface impedance is effectively reduced under the illumination condition, the electronic conductivity of the electrode material is increased, the capacity of the secondary battery is improved by more than 20%, and the solid-state thin-film battery is expected to be applied to the field of optical switches.

Description

Light-assisted enhanced secondary battery and preparation method thereof
Technical Field
The invention belongs to the technical field of solid-state batteries, and relates to a light-assisted enhanced secondary battery and a preparation method thereof.
Background
Among all energy storage technologies, the electrochemical energy storage technology has the characteristics of short construction period, capability of meeting different power grid function requirements and the like, and is one of the most widely used energy storage modes. The existing electrochemical energy storage technology has various technical routes, such as a lead-acid battery, a flow battery, a sodium-sulfur battery, a lithium ion battery and the like. However, these battery systems still fail to meet practical requirements in terms of a combination of cost, life, safety, environmental considerations, and the like.
At present, the solid-state thin-film lithium battery has the characteristics of being ultrathin, ultralight, high in safety, capable of being integrated, flexible and the like, and has a very wide application prospect in the fields of microsystems, foldable, wearable equipment, internet of things and the like. Therefore, all-solid-state thin film lithium batteries have attracted a great deal of attention. At present, the common preparation method of the all-solid-state thin-film lithium battery is to sequentially realize the deposition of the positive electrode and the current collector thin film, the electrolyte thin film, the negative electrode and the current collector thin film of the thin-film battery by adopting a chemical or physical vapor deposition technology, and finally complete the preparation of the thin-film battery. The magnetron sputtering technology has the obvious characteristics of high film growth rate, simple operation and the like, and is a mature technology for preparing the film battery.
Transition metal oxides have received much attention in the fields of supercapacitors, ion batteries, photocatalysis, etc. due to their specific structures and properties. Wherein, MoO3The method is especially researched due to the abundant minerals, low cost, simple synthetic method, stable performance and no pollution to the environment. Wherein the alpha phase MoO3Due to the special octahedral structure, a convenient channel is provided for the insertion and extraction of lithium ions in the lithium ion battery, and the lithium ion battery has attracted attention. The development and use of molybdenum and its oxides was reported by Isabella Alves de Castro et al, and MoO3The electrochemical performance is deeply researched, and the alpha-phase MoO3Has a theoretical specific capacity of about 310mAh/g (De Castro I A, Datta R S, Ou J Z, et al]Advanced Materials,2017: 1701619.). But at present, the capacity of the battery applied to a liquid or solid thin film battery is generally lower than the theoretical specific capacity. In addition, conventional solid-state batteries are typically fabricated on substrates of alumina, glass, stainless steel, and the like. Sun et al reported a MoO with a three-dimensional nanosheet structure3Solid state thin film powerA pool having a specific capacity of about 175mA/g (Sun S, Xia Q, Liu J, et al. self-standing oxygen-specific. alpha. -MoO3-x nanofilake arrays as 3D cathode for advanced all-soluble-state thin film batteries [ J S, Xia Q, Liu J, et al. Self-standing oxygen-specific. alpha. -MoO3-x nanofilake arrays [ J ] at a current density of 200mA/g].Journal of Materiomics,2019.)。
Disclosure of Invention
The invention aims to provide a light-assisted enhanced secondary battery with remarkably improved electrochemical performance under illumination and a preparation method thereof.
The technical scheme for realizing the purpose of the invention is as follows:
light-assisted enhanced secondary battery, FTO conductive glass as substrate, MoO3The film is used as a positive electrode, the lithium phosphorus oxygen nitrogen film is used as a solid electrolyte film, the metal Li film is used as a negative electrode, and the metal Cu is used as a negative electrode current collector.
The preparation method of the light-assisted enhanced secondary battery comprises the following specific steps:
adopting a magnetron sputtering method to deposit MoO on the surface of FTO conductive glass of a substrate3The film is used as a positive electrode film, then a lithium phosphorus oxygen nitrogen solid electrolyte film is deposited by adopting a magnetron sputtering technology, then a metal Li film is deposited by adopting a vacuum evaporation method to be used as a negative electrode, and finally Cu is deposited by adopting a magnetron sputtering method to be used as a negative electrode current collector.
Preferably, said MoO3The thickness of the film was 0.5. + -. 0.1. mu.m.
Preferably, the MoO is deposited by magnetron sputtering3The working parameters of the film are as follows: purity of>99 percent of high-purity metal Mo is used as a target material, and sputtering gas is high-purity Ar and high-purity O2The working pressure is 0.6Pa, and the sputtering power is 80W.
Preferably, the thickness of the lithium phosphorus oxygen nitrogen solid electrolyte film is 1.5-3 μm.
Preferably, the working parameters of the magnetron sputtering deposition lithium phosphorus oxygen nitrogen solid electrolyte film are as follows: purity of>99.9% high purity Li3PO4As target material, the sputtering gas is high-purity N2The working pressure is 0.9Pa, and the sputtering power is 90W.
Preferably, the thickness of the metal Li film is 2-3 μm.
Preferably, the working parameters of the magnetron sputtering deposition of Cu are as follows: high-purity Cu with the purity of more than 99.9 percent is used as a target material, the sputtering gas is high-purity Ar, the working pressure is 0.6Pa, and the sputtering power is 60W.
Compared with the prior art, the invention has the following advantages:
the invention prepares the transparent photoelectrode based on the FTO glass substrate by controlling MoO3The thickness of the film and the light transmittance are controlled, the interface impedance of the battery can be effectively reduced under the light compensation, the electronic conductivity of the electrode material is increased, the capacity of the battery is further improved, the theoretical specific capacity of the battery is increased from 165mAh/g in a dark environment to 195mAh/g under the illumination condition under the current density of 200mA/g, and the theoretical specific capacity is improved by about 17%.
Drawings
Fig. 1 is a schematic structural view of a photo-assisted enhanced secondary battery of the present invention, 1-glass, 2-FTO thin film, 3-positive thin film, 4-electrolyte thin film, 5-negative thin film, 6-negative current collector;
FIG. 2 shows the preparation of alpha-MoO by magnetron sputtering3A surface topography of the positive electrode film;
fig. 3 is a pictorial view of a light-assisted reinforced secondary battery of the present invention;
fig. 4 is a graph comparing specific capacity versus cycle number curves for light-assisted enhanced secondary batteries under dark and light compensation conditions.
Fig. 5 is a graph comparing EIS of light-assisted enhanced secondary batteries in dark and light conditions.
FIG. 6 is 1.0. mu. mMoO3The specific capacity-cycle number curve of the secondary battery prepared by the positive electrode film is compared with the specific capacity-cycle number curve under dark and light conditions.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
Example 1
The preparation of the light-assisted enhanced secondary battery comprises the steps of taking FTO (fluorine-doped tin oxide) conductive glass as a substrate, using a mask to perform masking, completing deposition of an anode film in a magnetron sputtering working chamber A, transferring a sample to a glove box to complete replacement of the mask, then transferring to a working chamber B to complete deposition of an electrolyte film, completing deposition of a metal cathode film in a chamber C, and then transferring to a chamber B to complete deposition of a cathode current collector. And finally, performing charge and discharge test on the light-assisted enhanced secondary battery in a glove box by adopting a LAND test system. The method comprises the following specific steps:
1. preparing an FTO-based conductive glass positive electrode film:
and (3) placing the FTO conductive glass in a working chamber A, and sputtering and depositing a positive film. Adopting a direct current reaction magnetron sputtering method and taking high-purity metal Mo as a target material (purity)>99%) of high-purity Ar and high-purity O2The working pressure is 0.6Pa, the sputtering power is 80W, and MoO is deposited by sputtering3The thickness of the anode film is controlled to be 0.5 +/-0.1 mu m.
2. Preparing a solid electrolyte film by magnetron sputtering:
transferring the sample to a working chamber B, continuously sputtering and depositing a solid electrolyte film, and adopting a magnetron sputtering method to prepare high-purity Li3PO4Is a target material (purity)>99.9%) and the sputtering gas is high-purity N2The working pressure is 0.9Pa, the sputtering power is 90W, and the LiPON film is sputtered and deposited, and the thickness is controlled to be 1.5-3 mu m.
3. Preparing a negative electrode film:
and transferring the sample to a working chamber, and continuing vacuum evaporation and deposition of the metallic Li cathode film. A vacuum evaporation method is adopted, a high-purity metal Li sheet is used as a raw material, a Li cathode film is evaporated and deposited, and the thickness is controlled to be 2-3 mu m. Then, the evaporation source was turned off, and the sample was taken out.
4. Preparing a negative current collector film:
and transferring the sample to a working chamber B, continuously sputtering and depositing a negative current collector film, and sputtering and depositing a Cu film with the thickness controlled to be about 0.5 mu m by adopting a magnetron sputtering method and taking high-purity metal Cu as a target material (the purity is more than 99.9%), sputtering gas is high-purity Ar, the working pressure is 0.6Pa, the sputtering power is 60W.
Electrochemical performance test of the photo-assisted enhanced secondary battery:
the battery sample of the invention is tested by adopting a LAND test system within the voltage range of 1.5-3.5V and at the voltage of 100mA/cm2A constant current charge-discharge cycle test shows that under the conditions of darkness and an external light source (485nm blue light LED), the battery is cycled for 100 times, the battery can be normally charged and discharged, the short circuit condition is not generated, the specific capacity can respectively reach 165mAh/g and 195mAh/g, and the specific capacity of the battery under the illumination condition is improved by about 20 percent, as shown in figure 4. In addition, as shown in fig. 5, the interface impedance of the light-assisted enhanced secondary battery is significantly reduced and the conductivity is improved under the illumination condition. The results show that the electrochemical performance of the photo-assisted enhanced secondary battery is remarkably improved under the condition of optical compensation.
Comparative example 1
This comparative example is essentially the same as example 1, except that MoO3The thickness of the positive electrode thin film was 1.0. mu.m. The specific capacities of the prepared secondary batteries under dark and light conditions are 125mAh/g and 145mAh/g respectively.

Claims (8)

1. The light-assisted reinforced secondary battery is characterized in that FTO conductive glass is used as a substrate, and MoO3The film is used as a positive electrode, the lithium phosphorus oxygen nitrogen film is used as a solid electrolyte film, the metal Li film is used as a negative electrode, and the metal Cu is used as a negative electrode current collector.
2. The method for preparing a photo-assisted enhanced secondary battery according to claim 1, comprising the following steps:
adopting a magnetron sputtering method to deposit MoO on the surface of FTO conductive glass of a substrate3The film is used as a positive electrode film, then a lithium phosphorus oxygen nitrogen solid electrolyte film is deposited by adopting a magnetron sputtering technology, then a metal Li film is deposited by adopting a vacuum evaporation method to be used as a negative electrode, and finally Cu is deposited by adopting a magnetron sputtering method to be used as a negative electrode current collector.
3. The method of claim 2, wherein said MoO is present in a liquid3The thickness of the film was 0.5. + -. 0.1. mu.m.
4. The method of claim 2 or 3, wherein the magnetron sputtering is performedJet deposition of MoO3The working parameters of the film are as follows: purity of>99 percent of high-purity metal Mo is used as a target material, and sputtering gas is high-purity Ar and high-purity O2The working pressure is 0.6Pa, and the sputtering power is 80W.
5. The preparation method according to claim 2, wherein the thickness of the lithium phosphorus oxygen nitrogen solid electrolyte film is 1.5 to 3 μm.
6. The preparation method according to claim 2 or 5, wherein the working parameters of the magnetron sputtering deposition of the lithium phosphorus oxygen nitrogen solid electrolyte film are as follows: purity of>99.9% high purity Li3PO4As target material, the sputtering gas is high-purity N2The working pressure is 0.9Pa, and the sputtering power is 90W.
7. The method according to claim 2, wherein the thickness of the metallic Li thin film is 2 to 3 μm.
8. The preparation method according to claim 2, wherein the working parameters of the magnetron sputtering deposition of Cu are as follows: high-purity Cu with the purity of more than 99.9 percent is used as a target material, the sputtering gas is high-purity Ar, the working pressure is 0.6Pa, and the sputtering power is 60W.
CN201910701482.6A 2019-07-31 2019-07-31 Light-assisted enhanced secondary battery and preparation method thereof Withdrawn CN112310468A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114552074A (en) * 2022-03-04 2022-05-27 哈尔滨工业大学 Polymer-based solid rechargeable metal-air battery capable of running at room temperature
CN115360358A (en) * 2022-08-24 2022-11-18 哈尔滨工业大学 All-solid-state lithium battery based on illumination excitation and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114552074A (en) * 2022-03-04 2022-05-27 哈尔滨工业大学 Polymer-based solid rechargeable metal-air battery capable of running at room temperature
CN115360358A (en) * 2022-08-24 2022-11-18 哈尔滨工业大学 All-solid-state lithium battery based on illumination excitation and application

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Application publication date: 20210202