CN115000354B - Preparation method and application of sandwich composite electrode - Google Patents
Preparation method and application of sandwich composite electrode Download PDFInfo
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- CN115000354B CN115000354B CN202210603323.4A CN202210603323A CN115000354B CN 115000354 B CN115000354 B CN 115000354B CN 202210603323 A CN202210603323 A CN 202210603323A CN 115000354 B CN115000354 B CN 115000354B
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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 27
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 52
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011888 foil Substances 0.000 claims abstract description 36
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 33
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000003825 pressing Methods 0.000 claims abstract description 17
- 229910018130 Li 2 S-P 2 S 5 Inorganic materials 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 238000004519 manufacturing process Methods 0.000 claims 2
- 210000001787 dendrite Anatomy 0.000 abstract description 7
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 238000000280 densification Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000010287 polarization Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 15
- 239000007787 solid Substances 0.000 description 12
- 238000005096 rolling process Methods 0.000 description 8
- 238000007796 conventional method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 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
- 238000012545 processing Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 238000002604 ultrasonography 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
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 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
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000012886 linear function Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 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
- 239000000126 substance 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
Classifications
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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, a lithium foil and a solid electrolyte, and pressing to form a sandwich structure electrode; (2) Carrying out ultrasonic treatment on the sandwich structure electrode to obtain the sandwich composite electrode; the conditions of the ultrasonic treatment are as follows: 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 each ultrasonic wave is 0.2-20 seconds. The preparation method provided by the invention realizes the dispersive and interdiffusion compact contact of the two interfaces between the lithium foil and the current collector and the solid electrolyte, reduces the resistance of the electrode interface, ensures that the interfaces on two sides of the lithium foil are in dispersive distribution densification, remarkably inhibits the phenomenon of lithium dendrite, reduces polarization in the charge and discharge 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
With the development of energy storage industry, people put higher demands on the safety, energy density and the like of lithium ion batteries. The energy density of conventional lithium ion batteries is limited by the capacity of the negative graphite (e.g., the capacity of conventional graphite negative electrodes is 372 mAh. G) -1 ) And dendrite phenomenon can appear in the circulation process of liquid electrolyte in graphite negative pole, and this not only can greatly reduced the life-span of battery, can also lead to the factor of safety of battery to reduce simultaneously. Sulfur-based solid state batteries have been extensively studied as a critical system to address the safety and lifetime of high specific energy batteries, but lowering the high charge transfer resistance of their electrode interfaces remains a major challenge.
In addition, the traditional lithium metal composite electrode mainly uses a mechanical pressure means to press the current collector and the lithium metal negative electrode into an integrated electrode, however, the interface contact of the prepared composite electrode is disordered and cannot be effectively regulated. It has been reported that the degree of non-uniformity of the interface structure is the source of localized deterioration of lithium dendrites. However, the related art reported so far is only to achieve a linear function type rigid interfacial contact of the interface of the composite current collector (e.g., copper foil) and lithium metal in the composite electrode, and there is no good means to densify the interface of the composite current collector (e.g., copper foil) and lithium metal in the composite electrode. In the prior art, the interface between lithium metal and electrolyte is optimized by adopting a chemical formation and welding method, and the prepared composite electrode still has serious lithium dendrite phenomenon, which is not beneficial to the improvement of the cycle stability and the rate capability of a lithium battery.
Therefore, it is needed to provide a new preparation method of lithium metal composite electrode, which significantly improves the lithium dendrite phenomenon of the composite electrode, and further improves the cycle stability and the rate capability of the lithium battery.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a preparation method and application of the sandwich composite electrode, wherein the preparation method can obviously weaken or eliminate the lithium dendrite phenomenon of the composite electrode, thereby improving the cycle stability and the rate capability of a lithium battery.
The invention is characterized in that: according to the invention, the current collector, the lithium foil and the solid electrolyte are pressed into the electrode slice under mechanical pressure according to a sandwich structure, and then the electrode slice is processed under specific ultrasonic processing conditions, so that the diffuse type and mutual diffusion compact contact of two interfaces between the lithium foil and the current collector and between the lithium foil and the solid electrolyte is realized, the resistance of the electrode interface is reduced, the interfaces on two sides of the lithium foil are subjected to diffuse distribution densification, the lithium dendrite phenomenon is obviously inhibited, the polarization in the charge and discharge process is reduced, and the multiplying power characteristic and the cycle stability of a battery (solid soft-package battery or laminated battery) are improved.
The first aspect of the invention provides a method for preparing a sandwich composite electrode.
Specifically, the preparation method of the sandwich composite electrode comprises the following steps:
(1) Sequentially stacking a current collector, a lithium foil and a solid electrolyte, and pressing to form a sandwich structure electrode;
(2) Carrying out ultrasonic treatment on the sandwich structure electrode to obtain 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 ultrasonic wave is 0.2-20 seconds.
Preferably, the number of ultrasonic repetitions is 2 to 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 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 each ultrasonic wave is 0.2-15 seconds.
Further 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 each ultrasonic wave 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., the lithium foil has a thickness of 20, 50, or 100 μm); further preferably, the lithium foil has a thickness of 20 to 100 μm; more preferably, the lithium foil has a thickness of 30-80 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 them.
Preferably, the mass ratio of the current collector to the lithium foil to 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 ultrasonic treatment process, the ratio of the time of turning on the ultrasonic wave to the time of turning off the ultrasonic wave is 1: (1-30); preferably 1: (1-20), for example, the ratio of the time that the ultrasound is on to the time that the ultrasound is off is 1: 1. 1: 2. 1: 3. 1: 5. 1: 10. 1:20.
preferably, the pressing process adopts a mechanical rolling mode to press.
Preferably, the gap between the two rollers is 20-240 μm in the pressing process by adopting a mechanical rolling mode; preferably 50-200 μm.
A second aspect of the invention provides a sandwich composite electrode.
The sandwich composite electrode is prepared by the preparation method.
The two interfaces between the lithium foil in the sandwich composite electrode and the current collector and the solid electrolyte have the compact contact characteristic of dispersion type 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 state pouch battery or a laminated battery.
Compared with the prior art, the invention has the following beneficial effects:
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, then the electrode sheet is processed under specific ultrasonic processing conditions (the ultrasonic frequency is 20KHz-50KHz, the ultrasonic power 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 each ultrasonic is 0.2-20 seconds, namely, the ultrasonic processing is performed by adopting pulse ultrasonic waves), so that the diffusion type mutual diffusion compact contact of the 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 interface diffusion distribution densification on the two sides of the lithium foil is obviously inhibited, the polarization in the charge and discharge process is reduced, and the multiplying power characteristic and the circulation stability of a battery (solid soft package battery or laminated battery) are improved.
Drawings
FIG. 1 is a scanning electron microscope image of the surface of a solid electrolyte in a sandwich composite electrode made in example 2 of the present invention;
FIG. 2 is an interfacial scanning electron microscope image of a sandwich composite electrode made in accordance with example 3 of the present invention;
FIG. 3 is an interfacial resistance diagram of a sandwich composite electrode in solid state soft pack batteries of examples 1-6 and comparative examples 1-2 of the present invention;
fig. 4 is a morphology diagram of a lithium foil surface of a sandwich composite electrode after charge-discharge cycle of the solid-state soft-pack battery obtained in example 6 of the present invention;
FIG. 5 is a graph showing the comparison of the rate performance of solid-state soft pack batteries of examples 3 to 6 according to the present invention;
FIG. 6 is a graph showing the comparison of the rate performance of solid-state soft pack batteries of examples 1-2 and comparative examples 1-2 according to the present invention;
FIG. 7 is a graph showing the comparison of the high rate cycle performance of the solid state soft pack batteries of comparative examples 1-2 and examples 1-2 in the present invention;
fig. 8 is a graph showing the comparison of the high rate cycle performance of the solid state soft pack batteries of examples 3 to 6 in 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 will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
In the following examples and comparative examples, the sandwich composite electrode was packaged into a solid state soft pack battery according to conventional methods.
Example 1: preparation of Sandwich composite electrode
A preparation method of a sandwich composite electrode comprises the following steps:
(1) Will collectFluid (copper foil), lithium foil (thickness of 20 μm), solid electrolyte (Li) 2 S-P 2 S 5 ) Sequentially stacked (mass ratio of current collector, lithium foil, solid electrolyte is 80:5:25 Pressing (the roller spacing of a roller press used in the pressing process is adjusted to be 100 mu m, and the rotating speed is adjusted to be 50 r/min) by adopting a mechanical rolling mode to form a sandwich structure electrode;
(2) Carrying out ultrasonic treatment on the sandwich structure electrode to obtain a sandwich composite electrode;
the conditions of the ultrasonic treatment are as follows: 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 seconds, and the time interval of each ultrasonic wave is 0.2 seconds.
The sandwich composite electrode prepared according to the embodiment of the conventional method is packaged into a solid-state soft-package battery.
Example 2: preparation of Sandwich composite electrode
A preparation method of a sandwich composite electrode comprises the following steps:
(1) A current collector (copper foil), a lithium foil (thickness of 20 μm), a solid electrolyte (Li 2 S-P 2 S 5 LiI) stacked in sequence (mass ratio of current collector, lithium foil, solid electrolyte 80:5:25 Pressing (the roller spacing of a roller press used in the pressing process is adjusted to be 100 mu m, and the rotating speed is adjusted to be 50 r/min) by adopting a mechanical rolling mode to form a sandwich structure electrode;
(2) Carrying out ultrasonic treatment on the sandwich structure electrode to obtain a sandwich composite electrode;
the conditions of the ultrasonic treatment are as follows: 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 seconds, and the time interval of each ultrasonic wave is 0.2 seconds.
The sandwich composite electrode prepared according to the embodiment of the conventional method is packaged into a solid-state soft-package battery.
Example 3: preparation of Sandwich composite electrode
A preparation method of a sandwich composite electrode comprises the following steps:
(1) A current collector (copper foil), a lithium foil (thickness of 20 μm), a solid electrolyte (Li 2 S-P 2 S 5 ) Sequentially stacked (mass ratio of current collector, lithium foil, solid electrolyte is 80:8:20 Pressing (the roller spacing of a roller press used in the pressing process is adjusted to be 100 mu m, and the rotating speed is adjusted to be 50 r/min) by adopting a mechanical rolling mode to form a sandwich structure electrode;
(2) Carrying out ultrasonic treatment on the sandwich structure electrode to obtain a sandwich composite electrode;
the conditions of the ultrasonic treatment are as follows: 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 seconds, and the time interval of each ultrasonic wave is 0.2 seconds.
The sandwich composite electrode prepared according to the embodiment of the conventional method is packaged into a solid-state soft-package battery.
Example 4: preparation of Sandwich composite electrode
A preparation method of a sandwich composite electrode comprises the following steps:
(1) A current collector (copper foil), a lithium foil (thickness of 20 μm), a solid electrolyte (Li 2 S-Li 2 S-P 2 S 5 -LI 2 O) are stacked in sequence (mass ratio of current collector, lithium foil, solid electrolyte is 80:5:25 Pressing (the roller spacing of a roller press used in the pressing process is adjusted to be 100 mu m, and the rotating speed is adjusted to be 50 r/min) by adopting a mechanical rolling mode to form a sandwich structure electrode;
(2) Carrying out ultrasonic treatment on the sandwich structure electrode to obtain a sandwich composite electrode;
the conditions of the ultrasonic treatment are as follows: the frequency of the ultrasonic wave is 20KHz, the power of the ultrasonic wave is 1000W, the ultrasonic wave is repeated 5 times, the time of each ultrasonic wave is 0.2 seconds, and the time interval of each ultrasonic wave is 1 second.
The sandwich composite electrode prepared according to the embodiment of the conventional method is packaged into a solid-state soft-package battery.
Example 5: preparation of Sandwich composite electrode
A preparation method of a sandwich composite electrode comprises the following steps:
(1) A current collector (copper foil), a lithium foil (thickness of 20 μm), a solid electrolyte (Li 2 S-Li 2 S-P 2 S 5 -LI 2 O) are stacked in sequence (mass ratio of current collector, lithium foil, solid electrolyte is 80:5:25 Pressing (the roller spacing of a roller press used in the pressing process is adjusted to be 100 mu m, and the rotating speed is adjusted to be 50 r/min) by adopting a mechanical rolling mode to form a sandwich structure electrode;
(2) Carrying out ultrasonic treatment on the sandwich structure electrode to obtain a sandwich composite electrode;
the conditions of the ultrasonic treatment are as follows: 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 seconds, and the time interval of each ultrasonic wave is 5 seconds.
The sandwich composite electrode prepared according to the embodiment of the conventional method is packaged into a solid-state soft-package battery.
Example 6: preparation of Sandwich composite electrode
A preparation method of a sandwich composite electrode comprises the following steps:
(1) A current collector (copper foil), a lithium foil (thickness of 20 μm), a solid electrolyte (Li 2 S-Li 2 S-P 2 S 5 -LI 2 O) are stacked in sequence (mass ratio of current collector, lithium foil, solid electrolyte is 80:4:26 Pressing (the roller spacing of a roller press used in the pressing process is adjusted to be 100 mu m, and the rotating speed is adjusted to be 50 r/min) by adopting a mechanical rolling mode to form a sandwich structure electrode;
(2) Carrying out ultrasonic treatment on the sandwich structure electrode to obtain a sandwich composite electrode;
the conditions of the ultrasonic treatment are as follows: 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 each ultrasonic wave is 15 seconds.
The sandwich composite electrode prepared according to the embodiment of the conventional method is packaged into a solid-state soft-package battery.
Comparative example 1
In comparison with example 1, the conditions of the ultrasonic treatment in comparative example 1 are: the frequency of the ultrasonic wave was 30KHz, the power of the ultrasonic wave was 1000W, the ultrasonic wave was 1 time, the ultrasonic time was 0.3 seconds, and the other procedures were the same as in example 1.
Comparative example 2
In comparison with example 1, the conditions of the ultrasonic treatment in comparative example 2 were: the frequency of the ultrasonic wave was 20KHz, the power of the ultrasonic wave was 800W, the ultrasonic wave was performed 3 times, the time of each ultrasonic wave was 1 second, the time interval of each ultrasonic wave was 0.1 second, and the other processes were the same as in example 1.
Product effect test
The solid state soft pack batteries prepared in examples 1-6 and comparative examples 1-2 were used for electrochemical impedance testing and electrochemical performance testing on an electrochemical workstation (model Solartron 1470E) and a battery testing system (model 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 made in example 2 of the present invention; FIG. 2 is an interfacial scanning electron microscope image of a sandwich composite electrode made in accordance with 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, and no void is generated, so that better close contact is formed.
FIG. 3 is an interfacial resistance graph of a sandwich composite electrode in solid state soft pack batteries of examples 1-6 and comparative examples 1-2 of the present invention (the original sample in FIG. 3 refers to the preparation of a sandwich composite electrode according to the method of example 1, but the process of preparation is not treated with ultrasonic waves, and the rest of the process is the same as in example 1); as can be seen from FIG. 3, the interface resistance of the solid-state soft-pack battery according to the embodiment of the invention is significantly lower than that of the solid-state soft-pack battery according to comparative examples 1-2, and particularly the interface resistance of the sandwich composite electrode in the solid-state soft-pack battery according to example 6 can be as low as 40Ω·cm -2 The sandwich composite electrode prepared according to the specific ultrasonic treatment condition of the invention is applied to a battery, and can obviously reduce interface resistance.
Fig. 4 is a morphology diagram of a lithium foil surface of a sandwich composite electrode after charge-discharge cycle of the solid-state soft-pack battery obtained in example 6 of the present invention; as can be seen from fig. 4, the interface of the sandwich composite electrode after ultrasonic treatment is tightly coupled and distributed, which is favorable for realizing uniform distribution of electric field lines and promoting uniform transmission of lithium ion flux, thereby realizing compact and flat deposition of lithium.
FIG. 5 is a graph showing the comparison of the rate performance of solid-state soft pack batteries of examples 3 to 6 according to the present invention; FIG. 6 is a graph showing the comparison of the rate performance of the solid-state soft pack batteries of comparative examples 1-2 and examples 1-2 in the present invention; as can be seen from fig. 5 to 6, the rate performance of the solid-state pouch cells of the examples of the present invention was significantly superior to that of the solid-state pouch cells of comparative examples 1 to 2. The sandwich composite electrode prepared by the embodiment of the invention is applied to a battery, and the battery has good cycling stability.
FIG. 7 is a graph showing the comparison of the high rate cycle performance of the solid state soft pack batteries of comparative examples 1-2 and examples 1-2 in the present invention; fig. 8 is a graph showing the comparison of the high rate cycle performance of the solid state soft pack batteries of examples 3 to 6 in the present invention. As can be seen from fig. 7 to 8, the solid-state soft-pack battery according to the embodiment of the present invention has significantly better high rate performance than the solid-state soft-pack battery according to comparative examples 1 to 2, as a result of constant current charge/discharge cycles performed at 3C. 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 (8)
1. The preparation method of the sandwich composite electrode is characterized by comprising the following steps of:
(1) Sequentially stacking a current collector, a lithium foil and a solid electrolyte, and pressing to form a sandwich structure electrode;
(2) Carrying out ultrasonic treatment on the sandwich structure electrode to obtain 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 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 each ultrasonic wave is 0.2-15 seconds.
2. The method of manufacturing according to claim 1, wherein the current collector is selected from at least one of copper foil, stainless steel, or carbon paper.
3. The method of manufacturing according to claim 1, wherein the solid electrolyte is a sulfur-based solid electrolyte.
4. The method of claim 1, wherein the solid electrolyte is selected from the group consisting of 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 them.
5. The method of claim 1, wherein the lithium foil has a thickness of 10-120 μm.
6. The preparation 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).
7. A sandwich composite electrode produced by the method of any one of claims 1-6.
8. A battery comprising the sandwich composite electrode of claim 7.
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