CN115000354A - Preparation method and application of sandwich composite electrode - Google Patents
Preparation method and application of sandwich composite electrode Download PDFInfo
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- CN115000354A CN115000354A CN202210603323.4A CN202210603323A CN115000354A CN 115000354 A CN115000354 A CN 115000354A CN 202210603323 A CN202210603323 A CN 202210603323A CN 115000354 A CN115000354 A CN 115000354A
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- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011888 foil Substances 0.000 claims abstract description 36
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 35
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000003825 pressing Methods 0.000 claims abstract description 17
- 229910018130 Li 2 S-P 2 S 5 Inorganic materials 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910018133 Li 2 S-SiS 2 Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Inorganic materials [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 abstract description 10
- 210000001787 dendrite Anatomy 0.000 abstract description 8
- 238000007599 discharging Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000010287 polarization Effects 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000000280 densification Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 22
- 210000004027 cell Anatomy 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- 238000005096 rolling process Methods 0.000 description 9
- 238000007796 conventional method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002905 metal composite material Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000012886 linear function Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention belongs to the technical field of batteries, and discloses a preparation method and application of a sandwich composite electrode. The preparation method comprises the following steps: (1) sequentially stacking a current collector, lithium foil and solid electrolyte, and pressing to form a sandwich structure electrode; (2) carrying out ultrasonic treatment on the electrode with the sandwich structure to prepare the sandwich composite electrode; the conditions of the ultrasonic treatment were: the frequency of the ultrasonic wave is 20KHz-50KHz, the ultrasonic wave is repeated for more than 2 times, the time of each ultrasonic wave is 0.2-8 seconds, and the time interval of every two ultrasonic waves is 0.2-20 seconds. The preparation method of the invention realizes the dispersion-type interdiffusion compact contact of two interfaces between the lithium foil and the current collector and the solid electrolyte, reduces the resistance of the electrode interface, ensures the dispersion distribution and the densification of the interfaces at two sides of the lithium foil, obviously inhibits the phenomenon of lithium dendrite, reduces the polarization in the charging and discharging process, and improves the multiplying power characteristic and the cycling stability of the battery.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a preparation method and application of a sandwich composite electrode.
Background
Along with the development of the energy storage industry, people have safety to lithium ion batteriesIn general, higher requirements are put on energy density and the like. The energy density of conventional lithium ion batteries is limited by the capacity limit of the negative graphite (e.g., 372mAh · g capacity of conventional graphite negative electrodes -1 ) And the graphite cathode has dendrite phenomenon in the circulation process of liquid electrolyte, which not only greatly reduces the service life of the battery, but also causes the safety coefficient of the battery to be reduced. Sulfur-based solid-state batteries have been extensively studied as a key system for solving the safety and lifespan of high-specific energy batteries, but it remains a great challenge to reduce the high charge transfer resistance at the electrode interface thereof.
In addition, the traditional lithium metal composite electrode mainly utilizes a mechanical pressure means to press a current collector and a lithium metal negative electrode into an integrated electrode, but the interface contact of the prepared composite electrode is disordered and cannot be effectively regulated and controlled. It has been reported that the degree of heterogeneity of the interface structure is the source of local deterioration of lithium dendrites. However, the related processes reported at present only achieve a linear-function type rigid interface contact of the interface between the composite current collector (e.g. copper foil) and the lithium metal in the composite electrode, and there is no better means for densifying the interface between the composite current collector (e.g. copper foil) and the lithium metal in the composite electrode. In the prior art, formation and welding means are usually adopted to optimize the interface of lithium metal and electrolyte, and the prepared composite electrode still has serious lithium dendrite phenomenon, which is not beneficial to the improvement of the cycle stability and rate capability of the lithium battery.
Therefore, it is desirable to provide a new method for preparing a lithium metal composite electrode, which significantly improves the lithium dendrite phenomenon of the composite electrode, and further improves the cycle stability and rate capability of the lithium battery.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a preparation method and application of a sandwich composite electrode, and the preparation method can obviously weaken or eliminate the lithium dendrite phenomenon of the composite electrode, thereby improving the cycle stability and rate capability of the lithium battery.
The invention conception of the invention is as follows: according to the invention, a current collector, a lithium foil and a solid electrolyte are pressed into an electrode sheet under mechanical pressure according to a sandwich structure, and then the electrode sheet is processed under a specific ultrasonic processing condition, so that the diffusion type interdiffusion compact contact of two interfaces between the lithium foil and the current collector and the solid electrolyte is realized, the resistance of the electrode interface is reduced, the interfaces on two sides of the lithium foil are diffused and distributed to be compact, the lithium dendrite phenomenon is obviously inhibited, the polarization in the charging and discharging process is reduced, and the multiplying power characteristic and the cycle stability of a battery (a solid soft package battery or a laminated battery) are improved.
In a first aspect of the invention, a method of making a sandwich composite electrode is provided.
Specifically, the preparation method of the sandwich composite electrode comprises the following steps:
(1) sequentially stacking a current collector, lithium foil and solid electrolyte, and pressing to form a sandwich structure electrode;
(2) carrying out ultrasonic treatment on the electrode with the sandwich structure to prepare the sandwich composite electrode;
the ultrasonic treatment conditions are as follows: the frequency of the ultrasonic wave is 20KHz-50KHz, the power of the ultrasonic wave is 1000W-3000W, the ultrasonic wave is repeated for more than 2 times, the time of each ultrasonic wave is 0.2-8 seconds, and the time interval of every two ultrasonic waves is 0.2-20 seconds.
Preferably, the number of ultrasound repetitions is 2-10.
Preferably, the ultrasonic treatment conditions are as follows: the frequency of the ultrasonic wave is 20KHz-50KHz, the power of the ultrasonic wave is 1000W-3000W, the number of ultrasonic repetition times is 2-5, the time of each ultrasonic is 0.2-5 seconds, and the time interval of every two ultrasonic is 0.2-15 seconds.
More preferably, the ultrasonic treatment conditions are as follows: the frequency of the ultrasonic wave is 20KHz-40KHz, the power of the ultrasonic wave is 1000W-3000W, the repeated times of the ultrasonic wave are 2-5 times, the time of each ultrasonic wave is 1-5 seconds, and the time interval of every two ultrasonic waves is 0.2-15 seconds.
Preferably, the current collector is selected from at least one of copper foil, stainless steel or carbon paper.
Preferably, the lithium foil has a thickness of 10-120 μm (e.g., a thickness of 20, 50, or 100 μm); further preferably, the thickness of the lithium foil is 20 to 100 μm; more preferably, the lithium foil has a thickness of 30 to 80 μm.
Preferably, the solid electrolyte is a sulfur-based solid electrolyte; further preferably, the solid electrolyte is selected from Li 2 S-P 2 S 5 、Li 2 S-P 2 S 5 -LiI、Li 2 S-Li 2 S-P 2 S 5 -LiCl、Li 2 S-Li 2 S-P 2 S 5 -LI 2 O、Li 2 S-SiS 2 At least one of (1).
Preferably, the mass ratio of the current collector, the lithium foil and the solid electrolyte is 80: (1-10): (10-45); further preferably, the mass ratio of the current collector, the lithium foil and the solid electrolyte is 80: (2-6): (14-38).
Preferably, in the process of performing ultrasonic treatment, the ratio of the time of turning on the ultrasound to the time of turning off the ultrasound is 1: (1-30); preferably 1: (1-20), for example, the ratio of the time of ultrasound on to the time of ultrasound off is 1: 1. 1: 2. 1: 3. 1: 5. 1: 10. 1: 20.
preferably, the pressing process adopts a mechanical rolling mode to perform pressing.
Preferably, the gap between two rollers is 20-240 μm during the pressing process by mechanical rolling; preferably 50-200. mu.m.
A second aspect of the invention provides a sandwich composite electrode.
The sandwich composite electrode is prepared by the preparation method.
Two interfaces among the lithium foil, the current collector and the solid electrolyte in the sandwich composite electrode have the compact contact characteristic of dispersion interdiffusion.
A third aspect of the invention provides the use of a sandwich composite electrode.
A battery comprises the sandwich composite electrode prepared by the method.
Preferably, the battery comprises a solid pouch battery or a laminated battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention presses the current collector, the lithium foil and the solid electrolyte into the electrode sheet under mechanical pressure according to a sandwich structure, then processing under specific ultrasonic processing conditions (the frequency of the ultrasonic wave is 20KHz-50KHz, the power of the ultrasonic wave is 1000W-3000W, the ultrasonic is repeated for more than 2 times, the time of each ultrasonic is 0.2-8 seconds, the time interval of every two times of ultrasonic is 0.2-20 seconds, namely, pulse ultrasonic processing is adopted), realizing the dispersion-type interdiffusion compact contact of two interfaces between the lithium foil and the current collector and the solid electrolyte, reducing the resistance of the electrode interface, densifying the interface dispersion distribution at two sides of the lithium foil, obviously inhibiting the lithium dendrite phenomenon, reducing the polarization in the charging and discharging process, and improving the rate characteristic and the cycle stability of the battery (a solid soft package battery or a laminated battery).
Drawings
FIG. 1 is a scanning electron microscope image of the surface of a solid electrolyte in a sandwich composite electrode prepared in example 2 of the present invention;
FIG. 2 is an interface scanning electron microscope image of a sandwich composite electrode prepared in example 3 of the present invention;
fig. 3 is a graph of the interfacial resistance of a sandwich composite electrode in solid state pouch cells of examples 1-6 of the present invention and comparative examples 1-2;
fig. 4 is a topography of the surface of a sandwich composite electrode lithium foil after charge-discharge cycling of the solid-state soft-package battery obtained in example 6 of the present invention;
fig. 5 is a graph comparing rate performance of solid pouch cells of examples 3-6 of the present invention;
fig. 6 is a graph comparing rate performance of solid state pouch cells of examples 1-2 and comparative examples 1-2 of the present invention;
fig. 7 is a graph comparing the high rate cycling performance of the solid state pouch cells of comparative examples 1-2 and examples 1-2 of the present invention;
fig. 8 is a graph comparing the high rate cycling performance of the solid state pouch cells of examples 3-6 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are, unless otherwise specified, either commercially available from conventional sources or can be obtained by known methods.
In the following examples and comparative examples, sandwich composite electrodes were packaged into solid pouch batteries according to conventional methods.
Example 1: preparation of sandwich composite electrode
A preparation method of a sandwich composite electrode comprises the following steps:
(1) current collector (copper foil), lithium foil (thickness 20 μm), solid electrolyte (Li) 2 S-P 2 S 5 ) And stacking the current collector, the lithium foil and the solid electrolyte in sequence (the mass ratio of the current collector to the lithium foil to the solid electrolyte is 80: 5: 25) pressing by adopting a mechanical rolling way (the distance between rollers of a rolling machine used in the pressing process is adjusted to be 100 mu m, and the rotating speed is adjusted to be 50r/min) to form the electrode with the sandwich structure;
(2) carrying out ultrasonic treatment on the electrode with the sandwich structure to prepare a sandwich composite electrode;
the conditions of the ultrasonic treatment were: the frequency of the ultrasonic wave is 20KHz, the power of the ultrasonic wave is 1000W, the ultrasonic wave is repeated for 2 times, the time of each ultrasonic wave is 0.2 second, and the time interval of every two ultrasonic waves is 0.2 second.
The sandwich composite electrode prepared in this example was packaged into a solid pouch cell according to conventional methods.
Example 2: preparation of sandwich composite electrode
A preparation method of a sandwich composite electrode comprises the following steps:
(1) current collector (copper foil), lithium foil (thickness 20 μm), solid electrolyte (Li) 2 S-P 2 S 5 LiI) are stacked in sequence (mass ratio of current collector, lithium foil, solid electrolyte 80: 5: 25) pressing by adopting a mechanical rolling mode (the distance between rollers of a roller press used in the pressing process is adjusted to be 100 mu m, the rotating speed is adjusted to be 50r/min),forming an electrode with a sandwich structure;
(2) carrying out ultrasonic treatment on the electrode with the sandwich structure to prepare a sandwich composite electrode;
the conditions of the ultrasonic treatment were: the frequency of the ultrasonic wave is 20KHz, the power of the ultrasonic wave is 2000W, the ultrasonic wave is repeated for 3 times, the time of each ultrasonic wave is 0.2 second, and the time interval of every two ultrasonic waves is 0.2 second.
The sandwich composite electrode prepared in this example was packaged into a solid pouch cell according to conventional methods.
Example 3: preparation of sandwich composite electrode
A preparation method of a sandwich composite electrode comprises the following steps:
(1) current collector (copper foil), lithium foil (thickness 20 μm), solid electrolyte (Li) 2 S-P 2 S 5 ) And stacking the current collector, the lithium foil and the solid electrolyte in sequence (the mass ratio of the current collector to the lithium foil to the solid electrolyte is 80: 8: 20) pressing by adopting a mechanical rolling mode (the distance between rollers of a roller press used in the pressing process is adjusted to be 100 mu m, and the rotating speed is adjusted to be 50r/min) to form an electrode with a sandwich structure;
(2) carrying out ultrasonic treatment on the electrode with the sandwich structure to obtain a sandwich composite electrode;
the conditions of the ultrasonic treatment were: the frequency of the ultrasonic wave is 30KHz, the power of the ultrasonic wave is 3000W, the ultrasonic wave is repeated for 2 times, the time of each ultrasonic wave is 0.2 second, and the time interval of every two ultrasonic waves is 0.2 second.
The sandwich composite electrode prepared in this example was packaged into a solid pouch cell according to conventional methods.
Example 4: preparation of sandwich composite electrode
A preparation method of a sandwich composite electrode comprises the following steps:
(1) current collector (copper foil), lithium foil (thickness 20 μm), solid electrolyte (Li) 2 S-Li 2 S-P 2 S 5 -LI 2 O) sequentially stacking (mass ratio of current collector, lithium foil, solid electrolyte 80: 5: 25) pressing by mechanical rolling (between rollers of a roller press used in the pressing process)Adjusting the distance to be 100 mu m and the rotating speed to be 50r/min) to form an electrode with a sandwich structure;
(2) carrying out ultrasonic treatment on the electrode with the sandwich structure to prepare a sandwich composite electrode;
the conditions of the ultrasonic treatment were: the frequency of the ultrasonic wave is 20KHz, the power of the ultrasonic wave is 1000W, the ultrasonic wave is repeated for 5 times, the time of each ultrasonic wave is 0.2 second, and the time interval of every two ultrasonic waves is 1 second.
The sandwich composite electrode prepared in this example was packaged into a solid pouch cell according to conventional methods.
Example 5: preparation of sandwich composite electrode
A preparation method of a sandwich composite electrode comprises the following steps:
(1) current collector (copper foil), lithium foil (thickness 20 μm), solid electrolyte (Li) 2 S-Li 2 S-P 2 S 5 -LI 2 O) sequentially stacking (mass ratio of current collector, lithium foil, solid electrolyte 80: 5: 25) pressing by adopting a mechanical rolling mode (the distance between rollers of a roller press used in the pressing process is adjusted to be 100 mu m, and the rotating speed is adjusted to be 50r/min) to form an electrode with a sandwich structure;
(2) carrying out ultrasonic treatment on the electrode with the sandwich structure to prepare a sandwich composite electrode;
the conditions of the ultrasonic treatment were: the frequency of the ultrasonic wave is 50KHz, the power of the ultrasonic wave is 1000W, the ultrasonic wave is repeated for 5 times, the time of each ultrasonic wave is 0.5 second, and the time interval of every two ultrasonic waves is 5 seconds.
The sandwich composite electrode prepared in this example was packaged into a solid pouch cell according to conventional methods.
Example 6: preparation of sandwich composite electrode
A preparation method of a sandwich composite electrode comprises the following steps:
(1) current collector (copper foil), lithium foil (thickness 20 μm), solid electrolyte (Li) 2 S-Li 2 S-P 2 S 5 -LI 2 O) sequentially stacking (mass ratio of current collector, lithium foil, solid electrolyte 80: 4: 26) by usingPressing in a mechanical rolling mode (the distance between rollers of a roller press used in the pressing process is adjusted to be 100 mu m, and the rotating speed is adjusted to be 50r/min) to form an electrode with a sandwich structure;
(2) carrying out ultrasonic treatment on the electrode with the sandwich structure to prepare a sandwich composite electrode;
the conditions of the ultrasonic treatment were: the frequency of the ultrasonic wave is 20KHz, the power of the ultrasonic wave is 1000W, the ultrasonic wave is repeated for 5 times, the time of each ultrasonic wave is 1.5 seconds, and the time interval of every two ultrasonic waves is 15 seconds.
The sandwich composite electrode prepared in this example was packaged into a solid pouch cell according to conventional methods.
Comparative example 1
Compared with example 1, the conditions of the ultrasonic treatment in comparative example 1 were: the frequency of the ultrasonic wave was 30KHz, the power of the ultrasonic wave was 1000W, the ultrasonic wave was performed 1 time, the ultrasonic time was 0.3 seconds, and the rest of the procedure was the same as in example 1.
Comparative example 2
Compared with example 1, the conditions of the ultrasonic treatment in comparative example 2 were: the frequency of the ultrasonic wave is 20KHz, the power of the ultrasonic wave is 800W, the ultrasonic wave is carried out for 3 times, the time of each ultrasonic wave is 1 second, the time interval of every two ultrasonic waves is 0.1 second, and the rest processes are the same as the example 1.
Product effectiveness testing
Electrochemical impedance tests and electrochemical performance tests were performed on the solid-state pouch cells prepared in examples 1-6 and comparative examples 1-2 on an electrochemical workstation (model number Solartron 1470E) and a cell test system (model number CT-4008-5V12 a-204). The impedance test frequency range is 0.01KHz-10MKHz, and the electrochemical test is a charge-discharge cycle test under different current densities.
FIG. 1 is a scanning electron microscope image of the surface of a solid electrolyte in a sandwich composite electrode prepared in example 2 of the present invention; FIG. 2 is an interface scanning electron microscope image of a sandwich composite electrode prepared in example 3 of the present invention; as can be seen from fig. 1-2, the interface between the lithium foil, the solid electrolyte and the current collector is diffusion-tightly coupled by ultrasonic treatment, no void is generated, and better close contact is formed.
Fig. 3 is a graph of interfacial resistance of a sandwich composite electrode in solid state pouch cells according to examples 1-6 of the present invention and comparative examples 1-2 (the original sample in fig. 3 refers to a sandwich composite electrode prepared according to the method of example 1, but without ultrasonic treatment, the rest of the process is the same as example 1); as can be seen from FIG. 3, the interfacial resistance of the solid-state laminate battery of the invention is significantly lower than that of the comparative examples 1-2, and particularly, the interfacial resistance of the sandwich composite electrode in the solid-state laminate battery of the invention of example 6 can be as low as 40 Ω -cm -2 It is shown that the sandwich composite electrode prepared according to the specific ultrasonic treatment conditions of the invention can significantly reduce the interface resistance when applied to a battery.
Fig. 4 is a topography of the surface of a sandwich composite electrode lithium foil after charge-discharge cycling of the solid-state soft-package battery obtained in example 6 of the present invention; as can be seen from fig. 4, the sandwich composite electrode interface subjected to ultrasonic treatment is tightly coupled and distributed, which is beneficial to realizing the uniform distribution of electric field lines and promoting the uniform transmission of lithium ion flux, thereby realizing the compact and flat deposition of lithium.
Fig. 5 is a graph comparing rate performance of solid pouch cells of examples 3-6 of the present invention; fig. 6 is a graph comparing rate performance of solid state pouch cells of comparative examples 1-2 and examples 1-2 in accordance with the present invention; as can be seen from fig. 5-6, the rate performance of the solid pouch cells of the examples of the present invention is significantly better than that of the solid pouch cells of comparative examples 1-2. The sandwich composite electrode prepared by the embodiment of the invention is applied to the battery, and the battery has good cycling stability.
Fig. 7 is a graph comparing the high rate cycling performance of the solid state pouch cells of comparative examples 1-2 and examples 1-2 of the present invention; fig. 8 is a graph comparing the high rate cycling performance of the solid state pouch cells of examples 3-6 of the present invention. In fig. 7-8, which are the results of constant current charge-discharge cycling at 3C, it can be seen from fig. 7-8 that the large rate performance of the solid-state pouch battery of the example of the invention is significantly better than the rate performance of the solid-state pouch battery of comparative examples 1-2. Further shows that the sandwich composite electrode prepared by the embodiment of the invention is applied to a battery, and the battery has good cycling stability.
Claims (10)
1. The preparation method of the sandwich composite electrode is characterized by comprising the following steps of:
(1) sequentially stacking a current collector, lithium foil and solid electrolyte, and pressing to form a sandwich structure electrode;
(2) carrying out ultrasonic treatment on the electrode with the sandwich structure to prepare the sandwich composite electrode;
the ultrasonic treatment conditions are as follows: the frequency of the ultrasonic wave is 20KHz-50KHz, the power of the ultrasonic wave is 1000W-3000W, the ultrasonic wave is repeated for more than 2 times, the time of each ultrasonic wave is 0.2-8 seconds, and the time interval of each two ultrasonic waves is 0.2-20 seconds.
2. The method of claim 1, wherein the ultrasound is repeated 2 to 10 times.
3. The method according to claim 1, wherein the ultrasonic treatment is performed under the following conditions: the frequency of the ultrasonic wave is 20KHz-50KHz, the power of the ultrasonic wave is 1000W-3000W, the repeated times of the ultrasonic wave are 2-5 times, the time of each ultrasonic wave is 0.2-5 seconds, and the time interval of every two ultrasonic waves is 0.2-15 seconds.
4. The method of claim 1, wherein the current collector is selected from at least one of copper foil, stainless steel, or carbon paper.
5. The production method according to claim 1, wherein the solid electrolyte is a sulfur-based solid electrolyte.
6. The production method according to claim 5, wherein the solid electrolyte is selected from Li 2 S-P 2 S 5 、Li 2 S-P 2 S 5 -LiI、Li 2 S-Li 2 S-P 2 S 5 -LiCl、Li 2 S-Li 2 S-P 2 S 5 -LI 2 O、Li 2 S-SiS 2 At least one of (1).
7. The method of claim 1, wherein the lithium foil has a thickness of 10 to 120 μm.
8. The production method according to claim 1, wherein the mass ratio of the current collector, the lithium foil, and the solid electrolyte is 80: (1-10): (10-45).
9. A sandwich composite electrode, characterized in that it is produced by the process according to any one of claims 1 to 8.
10. A battery comprising the sandwich composite electrode of claim 9.
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