CN111370627A - Direct compounding method of metal lithium electrode and inorganic solid electrolyte ceramic diaphragm - Google Patents
Direct compounding method of metal lithium electrode and inorganic solid electrolyte ceramic diaphragm Download PDFInfo
- Publication number
- CN111370627A CN111370627A CN202010235076.8A CN202010235076A CN111370627A CN 111370627 A CN111370627 A CN 111370627A CN 202010235076 A CN202010235076 A CN 202010235076A CN 111370627 A CN111370627 A CN 111370627A
- Authority
- CN
- China
- Prior art keywords
- lithium
- solid electrolyte
- ceramic diaphragm
- inorganic solid
- electrolyte ceramic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 126
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000000919 ceramic Substances 0.000 title claims abstract description 82
- 229910003480 inorganic solid Inorganic materials 0.000 title claims abstract description 51
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 47
- 239000002184 metal Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000013329 compounding Methods 0.000 title claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 50
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 claims description 13
- 238000005498 polishing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 230000002093 peripheral effect Effects 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001018 Cast iron Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 32
- 238000009736 wetting Methods 0.000 abstract description 8
- 230000008021 deposition Effects 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract 1
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 230000001351 cycling effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001453 impedance spectrum Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a direct compounding method of a metal lithium electrode and an inorganic solid electrolyte ceramic diaphragm, belonging to the fields of electrochemical engineering and ceramic industry. The method reduces the surface tension of the lithium liquid by increasing the melting temperature, and simultaneously destroys an oxide layer on the surface of the lithium liquid and air pits formed on the microscopic surface of the ceramic diaphragm due to unevenness by a friction mode, so that the fresh lithium liquid is directly contacted with the ceramic diaphragm body and is further soaked and spread, and the problems that the lithium liquid is difficult to soak on the surface of the ceramic diaphragm, the contact resistance of a metal lithium electrode and a solid/solid interface of the inorganic solid electrolyte ceramic diaphragm is large, the stability is poor and the like in the conventional method are solved. The method realizes the direct compounding of the metal lithium electrode and the inorganic solid electrolyte ceramic diaphragm without adopting the modes of atomic deposition and the like to pre-deposit a transition wetting layer on the surface of the ceramic diaphragm, has simple process flow, and is particularly suitable for a solid battery system taking metal lithium as a negative electrode and oxide inorganic solid electrolyte ceramic as the diaphragm.
Description
Technical Field
The invention relates to a method for compounding a metal lithium electrode and an inorganic solid electrolyte ceramic diaphragm, and belongs to the field of electrochemical engineering and ceramic industry.
Background
The lithium ion battery has the characteristics of high energy density, high specific power and the like, and is fast in development and wide in application. However, safety accidents such as combustion and explosion of lithium ion batteries occur in many ways from small mobile phones to medium-sized electric vehicles to large energy storage power stations, and the safety problem is undoubtedly a significant obstacle limiting the application of lithium ion batteries. The all-solid-state battery adopts ceramic inorganic solid electrolyte to replace inflammable and explosive organic electrolyte, is considered as an ultimate solution for the safety problem of the battery, can fundamentally solve the safety problem of the battery, and has become a common consensus of people for vigorously developing the solid-state battery technology although the difficulty is huge. The other great advantage brought by the improvement of the safety of the all-solid-state battery is that: the highest capacity lithium metal negative electrode can be used. At present, the 18650 battery capacity is improved to be more than 3.0Ah, the energy density exceeds 300Wh/kg and is close to the theoretical limit, the index of 500Wh/kg of the next generation is to be realized, under the condition of ensuring safety, the metal lithium with the lightest weight and the highest capacity is not the second choice of the cathode material, new systems such as lithium-sulfur, lithium-air and lithium metal batteries and the like all adopt the metal lithium cathode, and the corresponding solid-state battery technology is developed to be good.
The solid-state battery technology using the metallic lithium negative electrode meets the dual requirements of high safety and high energy density, but because no electrolyte exists, the problems of instability of a solid/solid interface, poor contact and large interface impedance exist between the inorganic electrolyte diaphragm and the metallic lithium negative electrode, and an organic electrolyte solution is generally adopted to wet the solid/solid interface as in the applied patent (CN201810697577.0) and the like. The mode of heating and melting metal lithium into lithium liquid and then compounding the lithium liquid with the inorganic solid electrolyte diaphragm is an important means for solving the solid/solid interface problem, but from the existing report, the inorganic solid electrolyte ceramic diaphragm prepared by the conventional method is prepared by LLZO (Li7La3Zr2O12) For example, the microstructure is usually small particles, multi-grain boundaries or porous, and the molten lithium cannot directly wet on the surface. For example, in Liangbing Hu et Al (Nature Materials, 2017, 16: 572-2O3Wetting layers to promote wetting with lithium solution, other transitional wetting layers they have attempted to include Si (Journal of the American Chemical Society, 2016, 138: 12258-. The method for depositing and modifying the wetting layer by the surface atoms inevitably further increases the process difficulty and the manufacturing cost of the battery and increases the difficulty of popularization and application. Furthermore, the reported cycling stability of Li | LLZO | Li symmetric batteries is not ideal, and there are still short lithium dendritesThe instability of the road and solid/solid interface. Such as the Li LLZO Li symmetrical battery assembled in sequence by Asma Sharaf et al at 0.05mA/cm2At the current density of (1 h/cycle), lithium dendrite short-circuit failure occurred only after 2 and 20 charge-discharge cycles (2016, 302: 135-; similarly, the Li | LLZO | Li symmetric cell obtained by Liangbinghu et al atomic deposition modification of ZnO (Nano Letters, 2017, 17: 565) -571) or Si (Journal of the American Chemical Society, 2016, 138: 12258-12262) was only at 0.1 and 0.05mA/cm, respectively2The current density of (2) is reported as 50 and 225 hours of cyclic charge and discharge (5-10 min/cycle).
Disclosure of Invention
The invention aims to solve the problem of solid/solid interface contact between a metallic lithium cathode and an inorganic solid electrolyte ceramic diaphragm when metallic lithium is adopted as the cathode in the solid-state battery technology, and provides a simple and feasible direct compounding method of the metallic lithium cathode and the inorganic solid electrolyte ceramic diaphragm.
The method for compounding the metal lithium electrode and the inorganic solid electrolyte ceramic diaphragm, which is adopted for solving the problems, comprises the following steps:
firstly, polishing and flattening the surfaces of two sides of an inorganic solid electrolyte ceramic diaphragm by adopting a 100-3000-mesh polishing sheet; then, under the protection of inert gas in a glove box, respectively placing an inorganic solid electrolyte ceramic diaphragm and a lithium melting pool on a temperature control heating table, and heating to 200-450 ℃ from room temperature at the speed of 2-20 ℃/min; adding a metal lithium sheet at the bottom of the lithium melting pool, and placing the preheated inorganic solid electrolyte ceramic diaphragm on the lithium liquid after the metal lithium sheet is melted into the lithium liquid; the bottom of the inorganic solid electrolyte ceramic diaphragm is in friction contact with the bottom plane of the lithium melting pool, the friction time is 3-300 seconds, an oxidation coating layer on the surface of the high-temperature lithium liquid is damaged, and the lithium liquid is soaked and spread on the surface of the inorganic solid electrolyte ceramic diaphragm; then taking out the inorganic solid electrolyte ceramic diaphragm with the molten lithium liquid on the two sides, and naturally cooling to room temperature to re-solidify the lithium liquid into metal lithium; polishing the peripheral edge of the inorganic solid electrolyte ceramic diaphragm to remove metal lithium adhered to the edge, and preventing short circuit between metal lithium electrodes on two sides of the inorganic solid electrolyte ceramic diaphragm; finally, placing the inorganic solid electrolyte ceramic diaphragm with metal lithium on two sides in a button cell shell, and packaging by adopting a button cell sealing machine to obtain the all-solid-state lithium-lithium symmetrical cell;
the bottom of the lithium melting tank is flat and is made of cast iron, stainless steel, copper or aluminum;
the inert gas is more than one of helium, argon and nitrogen.
The principle of the composite method of the metal lithium electrode and the inorganic solid electrolyte ceramic diaphragm comprises the following steps: the wettability of molten lithium is closely related to the surface states of the molten lithium and the ceramic diaphragm, the surface tension of the metal lithium liquid is large and the metal lithium liquid is usually coated with an oxide layer, and a microscopic surface of a rough or porous ceramic diaphragm has 'gas pits', which seriously hinders the direct contact of the metal lithium liquid and the oxide layer, so that the metal lithium liquid is easy to present in a non-wetting state; firstly, the melting temperature is increased to reduce the surface tension of the lithium liquid, and secondly, an oxide layer 'skin' coated on the surface of the lithium liquid and an 'air pit' formed on the surface of the ceramic diaphragm due to uneven micro-morphology are simultaneously damaged in a friction mode, so that fresh lithium liquid is contacted with the inorganic solid electrolyte body, and the lithium liquid is promoted to directly soak and spread on the surface of the inorganic solid electrolyte ceramic diaphragm.
The wettability of the molten lithium is closely related to the surface states of the molten lithium and the molten lithium, and the lithium liquid is a metal molten liquid and has large surface tension per se; the metal lithium sheet has strong reducibility, the surface of the metal lithium sheet is usually coated with an oxide layer, the lithium liquid obtained by high-temperature melting has stronger reducibility, and the surface of the lithium liquid is also usually coated with a 'crust' layer generated by oxidation; meanwhile, the surface of the ceramic diaphragm is microscopically rough and uneven, and an air pit exists; these factors seriously hinder the direct contact of the lithium liquid with the inorganic solid electrolyte ceramic body, thereby presenting a non-wetting state. Therefore, the key for wetting the molten lithium is to reduce the surface tension of the lithium liquid, to destroy the oxide layer 'skin' on the surface of the lithium liquid, and to reduce or destroy the 'air pit' on the surface of the ceramic diaphragm. Based on the thought, the method improves the temperature of the molten lithium liquid to reduce the surface tension of the molten lithium liquid, simultaneously destroys the crust layer of the lithium liquid and the air pits on the surface of the ceramic diaphragm by a simple friction contact mode, promotes the lithium liquid to be soaked and spread on the surface of the ceramic diaphragm, directly compounds the lithium liquid and the ceramic diaphragm without modification such as atomic deposition soaking layer on the surface of the ceramic diaphragm, and solves the problem of large contact impedance of a solid/solid contact interface between a metal lithium cathode and the ceramic diaphragm. Moreover, the solid/solid interface obtained by the natural infiltration mode also has excellent charge and discharge cycle stability, and the solid/solid interface between the metal lithium electrode and the ceramic diaphragm still keeps good stability when the cycle number is dry under the condition similar to the literature.
The invention has the beneficial effects that: the method improves the discovery that the molten lithium liquid and the inorganic solid electrolyte ceramic diaphragm represented by LLZO cannot be directly infiltrated, avoids the process flow that the surface of the ceramic diaphragm needs to be modified and infiltrated in advance in the traditional method, realizes the direct compounding of the molten lithium liquid and the ceramic diaphragm, solves the problems of large resistance and poor stability of a solid/solid contact interface between a metal lithium cathode and the ceramic diaphragm, and the like, and the assembled all-solid Li | LLZO | Li symmetrical battery is at 0.05mA/cm2Next, even thousands of hours of cycling without decay were performed, far beyond the literature reporting tens to hundreds of hours cycling under the same conditions.
Drawings
FIG. 1 photograph showing the appearance of an inorganic solid electrolyte ceramic separator
FIG. 2 inorganic solid electrolyte ceramic separator partially infiltrated with molten lithium solution
FIG. 3 inorganic solid electrolyte ceramic separator completely infiltrated with molten lithium solution
All-solid-state lithium-lithium symmetrical battery prepared in figure 4
In the figure: 1. ceramic diaphragm, 2. lithium liquid, 3. molten lithium pool.
FIG. 5 AC impedance Spectrum at initialization of all solid-state lithium-lithium symmetric Battery
In the figure: the ordinate Z' is the imaginary impedance, in Ω; the abscissa Z' is the real part impedance, in Ω.
FIG. 6 electrochemical cycling stability of all solid-state lithium-lithium symmetric cells
In the figure: the left ordinate is voltage in V; the right ordinate is current in units A; the abscissa is the test time in unit h.
FIG. 7 AC impedance spectrum of full solid-state lithium-lithium symmetric battery after 3500h charge-discharge cycle
In the figure: the ordinate Z' is the imaginary impedance, in Ω; the abscissa Z' is the real part impedance, in Ω.
Detailed Description
The invention is further illustrated by the following figures and examples.
Example 1
The 0.50mol Nb-doped LLZO inorganic solid electrolyte Ceramic diaphragm (1) prepared by the self-densification method has the specific preparation process shown in the Journal of the European Ceramic Society, 38: 5454-5462). Firstly, sequentially adopting 500-mesh, 1000-mesh and 3000-mesh diamond grinding discs to polish and polish in the air, removing the surface layer of the ceramic diaphragm 1 and flattening the two surfaces of the ceramic diaphragm 1 to obtain the ceramic diaphragm 1 with the thickness of about 1mm and the diameter of about 1.2cm, wherein the appearance of the ceramic diaphragm 1 is shown in figure 1; immediately transferring the ceramic diaphragm 1 into an argon-protected glove box after polishing; then, under the protection of Ar gas in a glove box, respectively placing the ceramic diaphragm 1 and the lithium melting pool 3 on a medium temperature control heating table, and heating the temperature from room temperature to 280 ℃ at the speed of about 10 ℃/min; adding a metal lithium sheet at the bottom of the lithium melting pool, soaking the preheated inorganic solid electrolyte ceramic diaphragm 1 into lithium liquid 2 by using a stainless steel forceps after the metal lithium sheet is melted into the lithium liquid 2, and pressing to enable the bottom of the inorganic solid electrolyte ceramic diaphragm 1 to be in contact with the bottom plane of the lithium melting pool 3 and to rub back and forth, wherein the rubbing time is about 5 seconds, and part of the lithium liquid 2 is adhered to the surface of the ceramic diaphragm 1, as shown in fig. 2; repeating the rubbing contact for several times until the lithium liquid 2 is completely soaked and spread on the surface of the ceramic diaphragm 1, as shown in fig. 3; taking out the inorganic solid electrolyte ceramic diaphragm 1 with the molten lithium liquid 2 on two sides, and naturally cooling to room temperature to re-solidify the lithium liquid 2 into metal lithium, as shown in fig. 4; polishing the peripheral edge of the inorganic solid electrolyte ceramic diaphragm 1 by adopting a file, removing metal lithium adhered to the edge, and testing the resistance between the metal lithium on two sides of the ceramic diaphragm 1 by adopting a universal meter to ensure that no short circuit occurs between the metal lithium on the two sides; and finally, placing the inorganic solid electrolyte ceramic diaphragm 1 with the metal lithium on two sides in a button cell shell, and packaging by adopting a button cell sealing machine to obtain the full-solid-state lithium-lithium symmetrical cell (Li | LLZO | Li).
Testing the solid/solid interface impedance between the metal lithium and the ceramic diaphragm 1 by adopting an alternating current impedance method, wherein the frequency range is 1 MHz-1 Hz, and the perturbation voltage is 10 mV; and a charge-discharge instrument is adopted to represent the electrochemical cycling stability of the solid/solid interface. The test temperatures were all room temperature. Initially, the impedance spectrum of the all-solid-state lithium-lithium symmetric battery is shown in fig. 5, the total impedance (the sum of the diameters of the two semicircular arcs) is about 900 Ω, the diaphragm impedance (the diameter of the left semicircular arc) is about 500 Ω, the interface impedance (the diameter of the right semicircular arc) is about 350 Ω, and the interface impedance value is equivalent to the performance of the all-solid-state lithium-lithium symmetric battery obtained by performing pre-modification on the LLZO surface by using an atomic deposition method and then performing infiltration with molten lithium liquid. The electrochemical cycling stability curves of the all-solid-state lithium-lithium symmetric cell are shown in FIG. 6 at 0.01 and 0.02mA/cm, respectively2Charging and discharging at current density for 1000 hr, and then 0.05mA/cm2Charging and discharging for 1500h under the current density, wherein the time of each charging and discharging cycle is 1h, and the total cycle is 3500 h; the results in FIG. 6 show that: the all-solid-state lithium-lithium symmetrical battery prepared by the invention has excellent cycling stability, and can still keep stable after being continuously charged and discharged for 3500 h; furthermore, starting from 2000h, at a current density of 0.05mA/cm2When the battery is charged and discharged in the next cycle, the voltage polarization curve is continuously narrowed and tends to be stable, which shows that the polarization overpotential of the battery is gradually reduced, and the performance of the battery is improved after the cycle. The impedance spectrum of the all-solid-state lithium-lithium symmetric battery after 3500h charge and discharge is shown in fig. 7, and comparing fig. 5 with fig. 7, it can be known that after 3500h charge and discharge, the internal impedance of the symmetric battery is further reduced, the total impedance is reduced from 900 Ω at the initial stage of the test to 370 Ω, the impedance of the diaphragm is reduced from 550 Ω (accounting for 61% of the total impedance) to 330 Ω (the remaining 60%), and the interface impedance between the diaphragm and the lithium metal is reduced from 350 Ω to 40 Ω (the remaining 11%). This indicates that the lithium metal in the symmetric cell is between the LLZO separator and the lithium metal in the cell as the cycling charge and discharge progressesThe solid/solid interface is further strengthened and no lithium dendrite shorting to failure occurs.
In the above example, the invention adopts a simple friction mode to realize the infiltration of the molten lithium liquid on the surface of the LLZO ceramic diaphragm, solves the problems that the lithium liquid is difficult to infiltrate on the surface of the inorganic solid electrolyte ceramic diaphragm and the contact impedance between the metal lithium electrode and the solid/solid interface of the inorganic solid electrolyte ceramic diaphragm is large, realizes the direct compounding of the metal lithium electrode and the inorganic solid electrolyte ceramic diaphragm, and has simple process flow. In addition, the prepared all-solid-state lithium-lithium symmetrical battery has extremely high solid/solid interface stability, realizes continuous charge and discharge cycles of more than 3500h, and is far beyond the cycle of dozens to hundreds of hours under the same charge and discharge system reported by the literature.
Claims (3)
1. A direct compounding method of a metal lithium electrode and an inorganic solid electrolyte ceramic diaphragm is characterized by comprising the following steps:
firstly, polishing and flattening the surfaces of two sides of an inorganic solid electrolyte ceramic diaphragm (1) by adopting a 100-3000-mesh polishing piece; then, under the protection of inert gas in a glove box, respectively placing an inorganic solid electrolyte ceramic diaphragm (1) and a lithium melting pool (3) on a temperature control heating table, and heating to 200-450 ℃ from room temperature at the speed of 2-20 ℃/min; adding a metal lithium sheet at the bottom of the lithium melting pool (3), and placing the preheated inorganic solid electrolyte ceramic diaphragm (1) on the lithium liquid (2) after the metal lithium sheet is melted into the lithium liquid (2); the bottom of the inorganic solid electrolyte ceramic diaphragm (1) is in friction contact with the bottom plane of the lithium melting pool (3) for 1-300 seconds, and an oxidation coating layer on the surface of the high-temperature lithium liquid (2) is damaged, so that the lithium liquid (2) is soaked and spread on the surface of the inorganic solid electrolyte ceramic diaphragm (1); then taking out the inorganic solid electrolyte ceramic diaphragm (1) with the molten lithium liquid (2) on the two sides, and naturally cooling to room temperature to solidify the lithium liquid (2) into metal lithium; polishing the peripheral edge of the inorganic solid electrolyte ceramic diaphragm (1), removing metal lithium adhered to the edge, and preventing short circuit between metal lithium electrodes on two sides of the inorganic solid electrolyte ceramic diaphragm (1); and finally, placing the inorganic solid electrolyte ceramic diaphragm (1) with the metal lithium on the two sides in a button cell shell, and packaging by adopting a button cell sealing machine to obtain the all-solid-state lithium-lithium symmetrical cell.
2. The direct compounding method of a metal lithium electrode and an inorganic solid electrolyte ceramic separator according to claim 1, wherein: the bottom of the lithium melting pool (3) is flat and is made of cast iron, stainless steel, copper or aluminum.
3. The direct compounding method of a metal lithium electrode and an inorganic solid electrolyte ceramic separator according to claim 1, wherein: the inert gas is more than one of helium, argon and nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010235076.8A CN111370627B (en) | 2020-03-27 | 2020-03-27 | Direct compounding method of metal lithium electrode and inorganic solid electrolyte ceramic diaphragm |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010235076.8A CN111370627B (en) | 2020-03-27 | 2020-03-27 | Direct compounding method of metal lithium electrode and inorganic solid electrolyte ceramic diaphragm |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111370627A true CN111370627A (en) | 2020-07-03 |
| CN111370627B CN111370627B (en) | 2022-09-23 |
Family
ID=71209279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010235076.8A Active CN111370627B (en) | 2020-03-27 | 2020-03-27 | Direct compounding method of metal lithium electrode and inorganic solid electrolyte ceramic diaphragm |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111370627B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112084627A (en) * | 2020-08-07 | 2020-12-15 | 合肥国轩高科动力能源有限公司 | A method for qualitatively characterizing the wettability of electrolytes |
| CN112164814A (en) * | 2020-09-29 | 2021-01-01 | 清华大学 | Preparation method of composite electrolyte layer of solid oxide fuel cell and solid oxide fuel cell |
| CN112448013A (en) * | 2020-11-29 | 2021-03-05 | 上海交通大学 | All-solid-state lithium battery structure and assembling method thereof |
| CN113193172A (en) * | 2021-04-28 | 2021-07-30 | 天津中能锂业有限公司 | High-temperature-resistant metal lithium negative electrode and preparation method and application thereof |
| CN113809390A (en) * | 2021-07-30 | 2021-12-17 | 福建巨电新能源股份有限公司 | Preparation method of composite negative electrode of lithium battery |
Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025094A (en) * | 1994-11-23 | 2000-02-15 | Polyplus Battery Company, Inc. | Protective coatings for negative electrodes |
| CN104269508A (en) * | 2014-09-30 | 2015-01-07 | 中航锂电（洛阳）有限公司 | Composite ceramic coating, lithium ion battery composite ceramic diaphragm and lithium ion battery |
| US20150171463A1 (en) * | 2013-12-12 | 2015-06-18 | Ut-Battelle, Llc | High conducting oxide - sulfide composite lithium superionic conductor |
| US20150249260A1 (en) * | 2012-09-14 | 2015-09-03 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | LITHIUM-SULPHUR (Li-S) BATTERY WITH HIGH CYCLE STABILITY AND METHOD FOR OPERATION THEREOF |
| CN106129466A (en) * | 2016-08-24 | 2016-11-16 | 上海交通大学 | Solid electrolyte of reduction and metal lithium electrode interface resistance and preparation method thereof |
| CN106384801A (en) * | 2016-10-09 | 2017-02-08 | 中国人民解放军63971部队 | Preparation method of oxide solid electrolyte diaphragm |
| US20170110701A1 (en) * | 2014-05-21 | 2017-04-20 | Lubrizol Advanced Materials, Inc. | Integrated electrode assembly |
| CN106898821A (en) * | 2017-03-16 | 2017-06-27 | 中国人民解放军63971部队 | A kind of lithium lanthanum niobium oxygen solid electrolyte diaphragm preparation method |
| WO2018024380A1 (en) * | 2016-08-04 | 2018-02-08 | Bayerische Motoren Werke Aktiengesellschaft | Method for producing an electrochemical cell comprising a lithium electrode, and electrochemical cell |
| CN108110217A (en) * | 2017-12-19 | 2018-06-01 | 成都亦道科技合伙企业（有限合伙） | A kind of solid state lithium battery composite negative pole and preparation method thereof |
| CN108346776A (en) * | 2018-02-08 | 2018-07-31 | 清华大学 | A kind of composition metal cathode of lithium of sandwich structure and preparation method thereof |
| CN108365259A (en) * | 2018-02-08 | 2018-08-03 | 南京大学 | A kind of lithium ion solid electrolyte and the preparation method and application thereof |
| CN108878959A (en) * | 2018-06-14 | 2018-11-23 | 北京工业大学 | A kind of preparation and its application of organo-mineral complexing solid electrolyte |
| US20190027780A1 (en) * | 2017-07-24 | 2019-01-24 | Microvast Power Systems Co., Ltd. | Inorganic solid electrolyte composite slurry, method for preparing, application and lithium-ion battery having the same |
| CN109768251A (en) * | 2019-01-08 | 2019-05-17 | 五邑大学 | A kind of preparation method of surface coating modified lithium battery cathode material |
| CN109786675A (en) * | 2018-12-28 | 2019-05-21 | 中国电子科技集团公司第十八研究所 | Interface modification method for metal lithium cathode of solid-state lithium battery |
| CN109841811A (en) * | 2019-01-09 | 2019-06-04 | 同济大学 | A kind of lithium base negative electrode material and the preparation method and application thereof for solid state battery |
| CN109920980A (en) * | 2019-02-18 | 2019-06-21 | 五邑大学 | A kind of preparation method of surface coating modified lithium battery metal lithium negative electrode |
| CN110890530A (en) * | 2019-10-30 | 2020-03-17 | 苏州大学 | Lithium metal secondary battery based on porous ceramic composite lithium metal anode and preparation method thereof |
-
2020
- 2020-03-27 CN CN202010235076.8A patent/CN111370627B/en active Active
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025094A (en) * | 1994-11-23 | 2000-02-15 | Polyplus Battery Company, Inc. | Protective coatings for negative electrodes |
| US20150249260A1 (en) * | 2012-09-14 | 2015-09-03 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | LITHIUM-SULPHUR (Li-S) BATTERY WITH HIGH CYCLE STABILITY AND METHOD FOR OPERATION THEREOF |
| US20150171463A1 (en) * | 2013-12-12 | 2015-06-18 | Ut-Battelle, Llc | High conducting oxide - sulfide composite lithium superionic conductor |
| US20170110701A1 (en) * | 2014-05-21 | 2017-04-20 | Lubrizol Advanced Materials, Inc. | Integrated electrode assembly |
| CN104269508A (en) * | 2014-09-30 | 2015-01-07 | 中航锂电（洛阳）有限公司 | Composite ceramic coating, lithium ion battery composite ceramic diaphragm and lithium ion battery |
| WO2018024380A1 (en) * | 2016-08-04 | 2018-02-08 | Bayerische Motoren Werke Aktiengesellschaft | Method for producing an electrochemical cell comprising a lithium electrode, and electrochemical cell |
| CN106129466A (en) * | 2016-08-24 | 2016-11-16 | 上海交通大学 | Solid electrolyte of reduction and metal lithium electrode interface resistance and preparation method thereof |
| CN106384801A (en) * | 2016-10-09 | 2017-02-08 | 中国人民解放军63971部队 | Preparation method of oxide solid electrolyte diaphragm |
| CN106898821A (en) * | 2017-03-16 | 2017-06-27 | 中国人民解放军63971部队 | A kind of lithium lanthanum niobium oxygen solid electrolyte diaphragm preparation method |
| US20190027780A1 (en) * | 2017-07-24 | 2019-01-24 | Microvast Power Systems Co., Ltd. | Inorganic solid electrolyte composite slurry, method for preparing, application and lithium-ion battery having the same |
| CN108110217A (en) * | 2017-12-19 | 2018-06-01 | 成都亦道科技合伙企业（有限合伙） | A kind of solid state lithium battery composite negative pole and preparation method thereof |
| CN108346776A (en) * | 2018-02-08 | 2018-07-31 | 清华大学 | A kind of composition metal cathode of lithium of sandwich structure and preparation method thereof |
| CN108365259A (en) * | 2018-02-08 | 2018-08-03 | 南京大学 | A kind of lithium ion solid electrolyte and the preparation method and application thereof |
| CN108878959A (en) * | 2018-06-14 | 2018-11-23 | 北京工业大学 | A kind of preparation and its application of organo-mineral complexing solid electrolyte |
| CN109786675A (en) * | 2018-12-28 | 2019-05-21 | 中国电子科技集团公司第十八研究所 | Interface modification method for metal lithium cathode of solid-state lithium battery |
| CN109768251A (en) * | 2019-01-08 | 2019-05-17 | 五邑大学 | A kind of preparation method of surface coating modified lithium battery cathode material |
| CN109841811A (en) * | 2019-01-09 | 2019-06-04 | 同济大学 | A kind of lithium base negative electrode material and the preparation method and application thereof for solid state battery |
| CN109920980A (en) * | 2019-02-18 | 2019-06-21 | 五邑大学 | A kind of preparation method of surface coating modified lithium battery metal lithium negative electrode |
| CN110890530A (en) * | 2019-10-30 | 2020-03-17 | 苏州大学 | Lithium metal secondary battery based on porous ceramic composite lithium metal anode and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| ASMA SHARAFI，等: "Surface Chemistry Mechanism of Ultra-Low Interfacial Resistance in the Solid-State Electrolyte Li7La3Zr2O12", 《CHEMISTRY OF MATERIALS》 * |
| 杨宏星: "铝合金压铸件常见缩孔、气孔与改进", 《模具制造》 * |
| 段惠等: "固态金属锂电池最新进展评述", 《储能科学与技术》 * |
| 胡策军等: "锂硫电池安全性问题现状及未来发展态势", 《储能科学与技术》 * |
| 赵鹏程，等: "自致密Li7La3Zr2O12陶瓷隔膜与金属锂之间的固-固界面研究", 《中国化学会第十三届全国分析化学年会论文集（一）》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112084627A (en) * | 2020-08-07 | 2020-12-15 | 合肥国轩高科动力能源有限公司 | A method for qualitatively characterizing the wettability of electrolytes |
| CN112084627B (en) * | 2020-08-07 | 2022-09-30 | 合肥国轩高科动力能源有限公司 | A method for qualitatively characterizing the wettability of electrolytes |
| CN112164814A (en) * | 2020-09-29 | 2021-01-01 | 清华大学 | Preparation method of composite electrolyte layer of solid oxide fuel cell and solid oxide fuel cell |
| CN112448013A (en) * | 2020-11-29 | 2021-03-05 | 上海交通大学 | All-solid-state lithium battery structure and assembling method thereof |
| CN113193172A (en) * | 2021-04-28 | 2021-07-30 | 天津中能锂业有限公司 | High-temperature-resistant metal lithium negative electrode and preparation method and application thereof |
| CN113193172B (en) * | 2021-04-28 | 2022-09-09 | 天津中能锂业有限公司 | High-temperature-resistant metal lithium negative electrode and preparation method and application thereof |
| CN113809390A (en) * | 2021-07-30 | 2021-12-17 | 福建巨电新能源股份有限公司 | Preparation method of composite negative electrode of lithium battery |
| CN113809390B (en) * | 2021-07-30 | 2022-10-18 | 福建巨电新能源股份有限公司 | Preparation method of composite negative electrode of lithium battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111370627B (en) | 2022-09-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111370627B (en) | Direct compounding method of metal lithium electrode and inorganic solid electrolyte ceramic diaphragm | |
| CN111900388B (en) | Zinc ion battery negative electrode material, preparation and application thereof | |
| CN110085910B (en) | All-solid-state lithium battery, garnet solid electrolyte and preparation method thereof | |
| CN113054241A (en) | Solid-state lithium battery and preparation method thereof | |
| CN113113567A (en) | Positive electrode with gradient potential distribution, lithium ion battery and preparation method and application thereof | |
| CN112825350B (en) | Pre-lithiation negative pole piece, preparation method thereof and lithium secondary battery | |
| CN110518278A (en) | Solid electrolyte with negative interface layer, preparation method and solid battery | |
| WO2023245960A1 (en) | Lithium-magnesium composite negative electrode and preparation method therefor, and lithium-sulfur battery and all-solid-state battery prepared therefrom | |
| CN108682796A (en) | Silicon-carbon negative electrode material coated by alloy substance and preparation method thereof | |
| CN112909433A (en) | Silicon monoxide/polyacrylic acid modified high-safety battery diaphragm and preparation method and application thereof | |
| CN102263240A (en) | Lithium-ion secondary battery, negative electrode, manufacturing method of negative electrode, and charging and discharging method | |
| CN214428670U (en) | Lithium ion battery capable of being charged at low temperature | |
| CN114284635A (en) | A kind of diaphragm modification method for lithium metal anode protection | |
| CN115863790A (en) | Preparation method of composite artificial SEI protective layer modified lithium metal cathode | |
| CN111952598B (en) | Negative plate, preparation method thereof and secondary battery | |
| CN111509195A (en) | Surface modification method of metal lithium negative electrode in all-solid-state lithium battery | |
| CN113113568A (en) | Negative electrode with gradient potential distribution, lithium ion battery and preparation method and application thereof | |
| CN111900373A (en) | Preparation method of lithium dendrite-resistant lithium metal battery cathode side separator material | |
| CN104882631A (en) | Method for improving uniform heat dispersion performance of lithium ion battery electrode piece | |
| CN113097562A (en) | Lithium borohydride-garnet type oxide composite solid electrolyte material and preparation method and application thereof | |
| CN116544356A (en) | Solid-state battery | |
| CN117039215A (en) | Formation method and lithium ion battery | |
| CN114976219A (en) | Solid electrolyte covering aluminum silicon layer and preparation method and application thereof | |
| CN108717973A (en) | A kind of original position double-coating silicon-carbon cathode material and preparation method thereof | |
| CN111193010B (en) | A lithium battery composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |