CN111081955A - In-situ preparation method of solid-state battery - Google Patents
In-situ preparation method of solid-state battery Download PDFInfo
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- CN111081955A CN111081955A CN201911325960.4A CN201911325960A CN111081955A CN 111081955 A CN111081955 A CN 111081955A CN 201911325960 A CN201911325960 A CN 201911325960A CN 111081955 A CN111081955 A CN 111081955A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 37
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- 239000010416 ion conductor Substances 0.000 claims abstract description 36
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- 229910021525 ceramic electrolyte Inorganic materials 0.000 claims abstract description 28
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- 239000003792 electrolyte Substances 0.000 claims abstract description 19
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- 238000000576 coating method Methods 0.000 claims abstract description 16
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- 238000010438 heat treatment Methods 0.000 claims description 30
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- 239000000843 powder Substances 0.000 claims description 12
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- 238000003756 stirring Methods 0.000 claims description 9
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- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
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- 238000005303 weighing Methods 0.000 claims description 5
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- 150000003949 imides Chemical class 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
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- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- MPEVJYZOMGDTTQ-UHFFFAOYSA-N 3-(dichloromethyl)oxetane Chemical compound ClC(Cl)C1COC1 MPEVJYZOMGDTTQ-UHFFFAOYSA-N 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 239000007770 graphite material Substances 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- UHHKSVZZTYJVEG-UHFFFAOYSA-N oxepane Chemical compound C1CCCOCC1 UHHKSVZZTYJVEG-UHFFFAOYSA-N 0.000 claims description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000009461 vacuum packaging Methods 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 6
- 230000001737 promoting effect Effects 0.000 abstract description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 230000033228 biological regulation Effects 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
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- 238000005457 optimization Methods 0.000 abstract description 2
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- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000084 colloidal system Substances 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 229910052786 argon Inorganic materials 0.000 description 9
- 229910001290 LiPF6 Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
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- 101150058243 Lipf gene Proteins 0.000 description 3
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- 230000009471 action Effects 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 3
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- 239000000126 substance Substances 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
- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Materials Engineering (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to an in-situ preparation method of a solid-state battery, which adopts a functional ion conductor ceramic composite diaphragm to replace a common diaphragm, uses a polymer monomer, lithium salt and an electrolyte additive as an electrolyte precursor, introduces the polymer monomer, the lithium salt and the electrolyte additive into a network structure formed by the functional ion conductor ceramic composite diaphragm, and prepares the solid-state battery in situ through interface regulation and optimization; the functional ion conductor ceramic composite diaphragm is prepared by mixing inorganic ceramic electrolyte and vinylidene fluoride-hexafluoropropylene polymer colloid liquid in proportion and is obtained by a wet coating method. The invention combines the functional ion conductor ceramic composite diaphragm with the high-ionic-conductivity sub-network with the electrolyte precursor capable of ring-opening polymerization, regulates and optimizes the interface of the battery, plays roles in improving the ionic conductivity, stabilizing the interface of the battery, promoting physical contact, preventing side reaction, promoting the uniform deposition of lithium and inhibiting the growth of lithium dendrite, and effectively improves the rate capability and cycle life of the solid-state battery.
Description
Technical Field
The invention belongs to the technical field of solid-state lithium batteries, and particularly relates to an in-situ preparation method of a solid-state battery.
Background
In the traditional lithium ion battery, most of the traditional lithium ion batteries adopt liquid electrolyte, and have the problems of easy leakage, easy volatilization, flammability, poor safety and the like, thereby hindering the improvement of the battery performance.
In recent years, solid-state lithium ion batteries have been developed rapidly, have unique advantages in safety, energy density and lithium dendrite inhibition, and have become a necessary way for the development of future lithium batteries. The solid electrolyte replaces electrolyte and a diaphragm, plays a role in conducting ions and blocking electrons, and has the unique advantages of high safety and simple structure; meanwhile, the high electrochemical stability of the solid electrolyte enables the solid electrolyte to have better compatibility with high specific energy electrodes.
However, the solid/solid interface is rigid contact, which causes the problems of large interfacial resistance and poor interfacial compatibility of the solid-state battery; meanwhile, the problems of generation and growth of lithium dendrites are also existed, which affects the exertion of battery capacity and the improvement of energy density, and even causes the internal short circuit and temperature surge of the battery, thus causing safety problems. The existing lithium ion battery can only reach the specific energy of 300Wh/kg at present, and in order to realize the development goal that the energy density of the solid-state battery is more than 400Wh/kg, the problem of the internal interface of the solid-state battery needs to be solved urgently.
The introduction of a modification layer at the electrode/electrolyte interface is currently a conventional approach to improve the interfacial compatibility of solid-state batteries. However, large-area interface modification is not easy to be uniform, resulting in poor battery consistency and complicated and difficult preparation process.
Disclosure of Invention
The invention aims to solve the problems of poor ion conductivity, poor interface contact, difficult battery assembly of the diaphragm in the solid-state battery and the growing of negative lithium dendrite and the increasing of interface impedance in the circulating process of the solid-state battery at present, thereby providing an in-situ preparation method of the solid-state battery.
In order to solve the problem of poor ion conductivity of the diaphragm in the solid-state battery, the invention adopts inorganic ceramic electrolyte and PVDF-HFP as raw materials to prepare the functional ion conductor ceramic composite diaphragm which has a high ion conductive sub-network and high electrochemical stability with an electrode material. In order to solve the problems of poor interface contact, difficult battery assembly and the like, a polymer monomer, lithium salt and an electrolyte additive are used as precursors, introduced into a network structure formed by a functional ion conductor ceramic composite diaphragm, and subjected to interface regulation and optimization to prepare the solid-state battery in situ.
The invention is realized in such a way that an in-situ preparation method of a solid-state battery comprises the following steps:
(1) mixing a polymer monomer, a lithium salt and an electrolyte additive according to the mass ratio of (60-85) to (5-15) to (10-25) on a heating plate, heating and uniformly stirring to obtain an electrolyte precursor;
(2) sequentially stacking the positive electrode, the functional ion conductor ceramic composite diaphragm and the negative electrode of the solid-state battery in an inert protective atmosphere to assemble a battery core;
(3) and placing the battery core in a stainless steel shell or an aluminum-plastic film, injecting a certain amount of electrolyte precursor into a network structure formed by the functional ion conductor ceramic composite diaphragm, applying a certain pressure, carrying out vacuum packaging, and heating for a certain time to obtain the in-situ polymerized solid battery.
In the above technical solution, preferably, the method for preparing the functional ion conductor ceramic composite membrane includes the following steps:
① weighing a certain amount of inorganic ceramic electrolyte, and dry-grinding in a ball-milling pot for a certain time to obtain inorganic ceramic electrolyte powder;
② preparing polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) polymer colloidal fluid;
③, mixing the ball-milled inorganic ceramic electrolyte powder with PVDF-HFP colloidal solution according to a certain mass ratio, and uniformly stirring to obtain inorganic ceramic electrolyte + PVDF-HFP mixed slurry;
④, coating the mixed slurry obtained in step ③ on a 0.05mm base film in a wet coating mode under an inert protective atmosphere, and then placing the base film on a heating plate to be heated and dried for a certain time to obtain the functional ion conductor ceramic composite diaphragm.
In the above technical solution, it is further preferable that the inorganic ceramic electrolyte is cubic phase Li7La3Zr2O12(LLZO), Fe-LLZO, Ga-LLZO, Al-LLZO, Sr-LLZO, Y-LLZO, Nb-LLZO, Ta-LLZO, W-LLZO, Sb-LLZO, Al-LLZO.
In the above technical solution, it is further preferable that, in the step ①, the ball milling rotation speed of the ball milling tank is 200-.
In the above technical solution, it is further preferable that in the step ③, the mass ratio of the inorganic ceramic electrolyte powder to the PVDF-HFP colloidal solution is (80-95): (5-20).
In the above technical solution, it is further preferable that in the step ④, the coating thickness of the mixed slurry is 0.1-0.2mm, the heating and drying temperature of the base film is 0-70 ℃, preferably 50-70 ℃, and the heating time of the base film is 12-48 hours, preferably 12-24 hours.
In the above technical scheme, preferably, the polymer monomer includes, but is not limited to, one or more of 1, 3-dioxolane, propylene oxide, oxetane, ethylene oxide, 3-dichloromethyloxetane, 2-methyltetrahydrofuran, oxepane and tetrahydrofuran.
In the above technical solution, preferably, the lithium salt includes, but is not limited to, one or more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium difluorooxalato borate, lithium bisoxalato borate, lithium bistrifluoromethylsulfonyl imide and lithium bisdifluorosulfonyl imide.
In the above technical solution, preferably, the electrolyte additive includes, but is not limited to, one or more of ethyl acetate, propylene carbonate, ethyl methyl carbonate, ethylene carbonate, vinylene carbonate, propylene sulfite, fluoroethylene carbonate, and dimethyl carbonate.
In the above technical solution, preferably, in the step (1), the heating temperature is 20 to 40 ℃, and the stirring time is 1 to 5 hours.
In the above technical solution, preferably, the positive electrode active material includes, but is not limited to, one of NCA, NCM811, and LCO, and the negative electrode material includes, but is not limited to, one of lithium metal, lithium alloy, silicon carbon, and graphite material.
In the above technical solution, preferably, in the step (3), the heating temperature of the solid-state battery is 30 to 60 ℃, and the heating time is 12 to 24 hours.
The invention has the advantages and positive effects that:
the in-situ preparation method of the solid-state battery adopts a brand new technical scheme, compared with the prior art, the method combines the functional ion conductor ceramic composite diaphragm with the high-ion conductive sub-network with the electrolyte precursor capable of opening ring polymerization, regulates and optimizes the interface of the battery, and plays roles in improving the ionic conductivity, stabilizing the interface of the battery, promoting physical contact, preventing side reaction, promoting uniform deposition of lithium and inhibiting growth of lithium dendrite; meanwhile, the inorganic ceramic electrolyte LLZO in the composite diaphragm has good chemical stability, does not generate oxidation-reduction reaction with a negative electrode material, and has higher electrochemical decomposition voltage. Compared with other polymer matrixes, the polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) has relatively high ionic conductivity, good mechanical strength and excellent film forming performance.
Drawings
Fig. 1 is a cycle count-capacity and efficiency curve of an in-situ prepared solid-state battery provided in example 1 of the present invention;
FIG. 2 is a charge-discharge curve diagram of a Li/Li symmetrical battery prepared in situ by using a functional ion conductor ceramic composite diaphragm as a battery diaphragm according to comparative example 1 of the present invention;
FIG. 3 is a charge-discharge curve diagram of a Li/Li symmetrical battery prepared in situ by using a celgard diaphragm as a battery diaphragm according to comparative example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Under the protective atmosphere of high-purity argon, preparing the functional ion conductor ceramic composite diaphragm, which comprises the following steps:
weighing 2g of inorganic ceramic electrolyte, placing the inorganic ceramic electrolyte in a ball milling tank for dry milling at the ball milling rotation speed of 300r/min for 30min to obtain oxide solid electrolyte powder. And mixing the ball-milled inorganic ceramic electrolyte powder and the PVDF-HFP colloidal solution according to the mass ratio of 92:8, and uniformly stirring to obtain the inorganic ceramic electrolyte + PVDF-HFP mixed slurry. And coating the mixed slurry on a 0.05mm base film in a wet coating mode under the protection atmosphere of high-purity argon, wherein the coating thickness is 0.1mm, then placing the base film on a heating plate, heating and drying at the temperature of 60 ℃ for 12h, and preparing the functional ion conductor ceramic composite diaphragm for later use.
Under the protection atmosphere of high-purity argon, the solid-state battery is prepared in situ, and the method comprises the following steps:
1, 3-Dioxolane (DOL) and lithium hexafluorophosphate (LiPF) are added under the protection of high-purity argon6) And dimethyl carbonate (DMC) are mixed according to the mass ratio of 70:10:20, and the mixture is stirred for 2 hours on a heating plate at the temperature of 30 ℃ to obtain an electrolyte precursor.
As NCM811 (positive electrode active material): super P (conductive agent): PVDF (binder) ═ 90: 5: 5, preparing a positive electrode of the solid-state battery, and adopting metal lithium as a negative electrode. Sequentially stacking a positive electrode, a functional ion conductor ceramic composite diaphragm and negative electrode lithium, placing the stacked positive electrode, the functional ion conductor ceramic composite diaphragm and the negative electrode lithium in a stainless steel shell or an aluminum-plastic film, injecting a certain amount of electrolyte precursor, filling the electrolyte precursor into a network structure formed by the functional ion conductor ceramic composite diaphragm, and then carrying out cell pairingPressurizing, vacuum sealing, heating at 60 deg.C for 12 hr, and heating with DOL in LiPF6The in-situ ring-opening polymerization is automatically carried out under the action of the positive and negative electrodes, and the in-situ polymerization solid-state battery is obtained by regulating and controlling the positive and negative electrode interfaces. The solid-state battery is charged and discharged at a multiplying power of 0.1C under a voltage of 2.5-4.2V, test data are shown in figure 1, and it can be seen from figure 1 that the discharge specific capacity of the first circle of the obtained in-situ polymerization solid-state battery is 181.1mAh/g, the cycle is 100 circles, the discharge specific capacity is kept at 96.5%, and the average coulomb efficiency is 99.7%.
Example 2
Under the protective atmosphere of high-purity argon, preparing the functional ion conductor ceramic composite diaphragm, which comprises the following steps:
weighing 2g of inorganic ceramic electrolyte, placing the inorganic ceramic electrolyte in a ball milling tank for dry milling, wherein the ball milling rotation speed is 200r/min, and the ball milling time is 60min, so as to obtain oxide solid electrolyte powder. And mixing the inorganic ceramic electrolyte powder subjected to ball milling with the PVDF-HFP colloidal solution according to the mass ratio of 85:15, and uniformly stirring to obtain the inorganic ceramic electrolyte + PVDF-HFP mixed slurry. And coating the mixed slurry on a 0.05mm base film in a wet coating mode under the protection atmosphere of high-purity argon, wherein the coating thickness is 0.1mm, then placing the base film on a heating plate, heating and drying at the temperature of 50 ℃ for 24 hours, and preparing the functional ion conductor ceramic composite diaphragm for later use.
Under the protection atmosphere of high-purity argon, the solid-state battery is prepared in situ, and the method comprises the following steps:
1, 3-Dioxolane (DOL) and lithium hexafluorophosphate (LiPF) are added under the protection of high-purity argon6) And dimethyl carbonate (DMC) are mixed according to the mass ratio of 75:10:15, and the mixture is stirred for 2 hours on a heating plate at the temperature of 30 ℃ to obtain an electrolyte precursor.
As NCM811 (positive electrode active material): super P (conductive agent): PVDF (binder) ═ 90: 5: 5, preparing a positive electrode of the solid-state battery, and adopting metal lithium as a negative electrode. Sequentially stacking a positive electrode, a functional ion conductor ceramic composite diaphragm and negative electrode lithium, placing the stacked positive electrode, the functional ion conductor ceramic composite diaphragm and the negative electrode lithium in a stainless steel shell or an aluminum-plastic film, injecting a certain amount of electrolyte precursor, and filling a network junction formed by the functional ion conductor ceramic composite diaphragmAfter the structure, the battery is pressurized, sealed in vacuum and heated at 50 ℃ for 24h, DOL is in LiPF6The in-situ ring-opening polymerization is automatically carried out under the action of the positive and negative electrodes, and the in-situ polymerization solid-state battery is obtained by regulating and controlling the positive and negative electrode interfaces. The obtained solid-state battery is charged and discharged at a multiplying power of 0.1C under the voltage of 2.5-4.2V, the specific discharge capacity of the first circle is 170mAh/g, the cycle is 100 circles, the specific discharge capacity is kept at 93.2%, and the average coulombic efficiency is 99.2%.
Example 3
Under the protective atmosphere of high-purity argon, preparing the functional ion conductor ceramic composite diaphragm, which comprises the following steps:
weighing 2g of inorganic ceramic electrolyte, placing the inorganic ceramic electrolyte in a ball milling tank for dry milling, wherein the ball milling rotation speed is 200r/min, and the ball milling time is 60min, so as to obtain oxide solid electrolyte powder. And mixing the inorganic ceramic electrolyte powder subjected to ball milling with the PVDF-HFP colloidal solution according to a mass ratio of 90:10, and uniformly stirring to obtain inorganic ceramic electrolyte + PVDF-HFP mixed slurry. And coating the mixed slurry on a 0.05mm base film in a wet coating mode under the protection atmosphere of high-purity argon, wherein the coating thickness is 0.1mm, then placing the base film on a heating plate, heating and drying at the temperature of 50 ℃ for 24 hours, and preparing the functional ion conductor ceramic composite diaphragm for later use.
Under the protection atmosphere of high-purity argon, the solid-state battery is prepared in situ, and the method comprises the following steps:
1, 3-Dioxolane (DOL) and lithium hexafluorophosphate (LiPF) are added under the protection of high-purity argon6) And dimethyl carbonate (DMC) are mixed according to the mass ratio of 80:5:15, and the mixture is stirred for 2 hours on a heating plate at the temperature of 30 ℃ to obtain an electrolyte precursor.
As NCM811 (positive electrode active material): super P (conductive agent): PVDF (binder) ═ 90: 5: 5, preparing a positive electrode of the solid-state battery, and adopting metal lithium as a negative electrode. Sequentially stacking a positive electrode, a functional ion conductor ceramic composite diaphragm and negative electrode lithium, placing the stacked positive electrode, the functional ion conductor ceramic composite diaphragm and the negative electrode lithium in a stainless steel shell or an aluminum-plastic film, injecting a certain amount of electrolyte precursor, filling the electrolyte precursor into a network structure formed by the functional ion conductor ceramic composite diaphragm, pressurizing and vacuum sealing the battery, and heating to 50 DEG CHeating for 24h, DOL in LiPF6The in-situ ring-opening polymerization is automatically carried out under the action of the positive and negative electrodes, and the in-situ polymerization solid-state battery is obtained by regulating and controlling the positive and negative electrode interfaces. The obtained solid-state battery is charged and discharged at 2.5-4.2V and 0.1C multiplying power, the specific discharge capacity of the first circle is 173.5mAh/g, the specific discharge capacity is maintained at 94.1% after 100 circles of circulation, and the average coulombic efficiency is 99.5%.
Comparative example 1
The same in-situ solid-state battery preparation method as that of example 1 is adopted, and a Li/Li symmetrical battery is assembled by respectively taking a functional ion conductor ceramic composite diaphragm and a Celgard diaphragm as battery diaphragms, wherein the current density is 0.1mA/cm2And carrying out an electrochemical stability test. Wherein, the Li-functional ion conductor ceramic composite diaphragm + LiPF6The test data of the/Dol-Li symmetrical battery is shown in FIG. 2, and Li-cell grid diaphragm + LiPF6The test data for the/Dol-Li symmetric cell is shown in fig. 3. As can be seen from FIGS. 2 and 3, the polymer is bonded to a Li-celgard separator + LiPF6Compared with a Dol-Li symmetrical battery, after circulation for 40 hours, the Li-functional ion conductor ceramic composite diaphragm + LiPF6the/Dol-Li symmetrical battery shows stable circulation, which shows that the functional ion conductor ceramic composite diaphragm has certain inhibiting effect on the formation of lithium dendrite.
The inorganic ceramic electrolyte has high ionic conductivity, and the prepared functional ionic conductor ceramic composite diaphragm has proper aperture and porosity, can improve the affinity of in-situ polymerization precursor solution and increase the liquid absorption and retention capacity; the solid-state battery prepared by in-situ polymerization can solve the problems of difficult assembly, interface compatibility, leakage, short circuit and the like of the high-capacity solid-state battery caused by the traditional organic electrolyte. The preparation method simplifies the preparation process of the solid-state battery, has high safety, can form a stable solid-state electrolyte interface in the solid-state battery, realizes interface fusion and reduces interface impedance; the process flow and the equipment are similar to those of the traditional electrolyte battery, are easy to produce and prepare in a large-scale and industrialized mode, and can be used as a candidate for the advantages of a high-capacity solid battery.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: it is to be understood that modifications may be made to the technical solutions described in the foregoing embodiments, or some or all of the technical features may be equivalently replaced, and the modifications or the replacements may not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. An in-situ preparation method of a solid-state battery is characterized by comprising the following steps: comprises the following steps:
(1) mixing a polymer monomer, a lithium salt and an electrolyte additive according to the mass ratio of (60-85) to (5-15) to (10-25) on a heating plate, heating and uniformly stirring to obtain an electrolyte precursor;
(2) sequentially stacking the positive electrode, the functional ion conductor ceramic composite diaphragm and the negative electrode of the solid-state battery in an inert protective atmosphere to assemble a battery core;
(3) and placing the battery core in a stainless steel shell or an aluminum-plastic film, injecting a certain amount of electrolyte precursor into a network structure formed by the functional ion conductor ceramic composite diaphragm, applying a certain pressure, carrying out vacuum packaging, and heating for a certain time to obtain the in-situ polymerized solid battery.
2. The in-situ preparation method of a solid-state battery according to claim 1, characterized in that: the preparation method of the functional ion conductor ceramic composite diaphragm comprises the following steps:
① weighing a certain amount of inorganic ceramic electrolyte, and dry-grinding in a ball-milling pot for a certain time to obtain inorganic ceramic electrolyte powder;
② preparing polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) polymer colloidal fluid;
③, mixing the ball-milled inorganic ceramic electrolyte powder with PVDF-HFP colloidal solution according to a certain mass ratio, and uniformly stirring to obtain inorganic ceramic electrolyte + PVDF-HFP mixed slurry;
④, coating the mixed slurry obtained in step ③ on a 0.05mm base film in a wet coating mode under an inert protective atmosphere, and then placing the base film on a heating plate to be heated and dried for a certain time to obtain the functional ion conductor ceramic composite diaphragm.
3. The in-situ preparation method of a solid-state battery according to claim 2, characterized in that: the inorganic ceramic electrolyte is cubic phase Li7La3Zr2O12(LLZO), Fe-LLZO, Ga-LLZO, Al-LLZO, Sr-LLZO, Y-LLZO, Nb-LLZO, Ta-LLZO, W-LLZO, Sb-LLZO, Al-LLZO.
4. The in-situ preparation method of the solid-state battery according to claim 2, wherein in the step ①, the ball milling speed of the ball milling pot is 200-400r/min, and the ball milling time is 30-120 min.
5. The in-situ preparation method of a solid-state battery according to claim 2, wherein in the step ③, the mass ratio of the inorganic ceramic electrolyte powder to the PVDF-HFP colloidal solution is (80-95): 5-20).
6. The in-situ preparation method of the solid-state battery according to claim 2, wherein in the step ④, the coating thickness of the mixed slurry is 0.1-0.2mm, the heating and drying temperature of the base film is 0-70 ℃, and the heating time of the base film is 12-48 h.
7. The in-situ preparation method of a solid-state battery according to claim 1, characterized in that: the polymeric monomer includes, but is not limited to, one or more combinations of 1, 3-dioxolane, propylene oxide, oxetane, ethylene oxide, 3-dichloromethyloxetane, 2-methyltetrahydrofuran, oxepane, and tetrahydrofuran;
the lithium salt comprises but is not limited to one or more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium difluorooxalato borate, lithium bis-oxalato borate, lithium bis-trifluoromethylsulfonyl imide and lithium bis-difluorosulfonyl imide;
the electrolyte additive includes but is not limited to one or more of ethyl acetate, propylene carbonate, ethyl methyl carbonate, ethylene carbonate, vinylene carbonate, propylene sulfite, fluoroethylene carbonate and dimethyl carbonate.
8. The in-situ preparation method of a solid-state battery according to claim 1, characterized in that: in the step (1), the heating temperature is 20-40 ℃, and the stirring time is 1-5 h.
9. The in-situ preparation method of a solid-state battery according to claim 1, characterized in that: the positive active material includes but is not limited to one of NCA, NCM811 and LCO, and the negative active material includes but is not limited to one of lithium metal, lithium alloy, silicon carbon and graphite material.
10. The in-situ preparation method of a solid-state battery according to claim 1, characterized in that: in the step (3), the heating temperature of the solid-state battery is 30-60 ℃, and the heating time is 12-24 h.
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