CN113823768B - Preparation method of solid-state battery - Google Patents
Preparation method of solid-state battery Download PDFInfo
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- CN113823768B CN113823768B CN202110994311.4A CN202110994311A CN113823768B CN 113823768 B CN113823768 B CN 113823768B CN 202110994311 A CN202110994311 A CN 202110994311A CN 113823768 B CN113823768 B CN 113823768B
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- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000003792 electrolyte Substances 0.000 claims abstract description 52
- 150000003839 salts Chemical class 0.000 claims abstract description 41
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000006258 conductive agent Substances 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000011888 foil Substances 0.000 claims abstract description 8
- 238000005096 rolling process Methods 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 8
- 239000007774 positive electrode material Substances 0.000 claims abstract description 5
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910010941 LiFSI Inorganic materials 0.000 claims description 6
- 239000006183 anode active material Substances 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- H01M4/0409—Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
-
- 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
- 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
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- 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
- H01M2004/028—Positive 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
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- 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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of chemical power supplies, and particularly relates to a preparation method of a solid-state battery. The method comprises the following steps: adding a solvent and a binder into a homogenizing container, fully stirring and dissolving, and then adding a conductive agent and positive electrode active material powder, wherein the positive electrode active material powder accounts for 50-99 wt% of the solid content of the slurry; coating the evenly stirred slurry on an aluminum foil, wherein the coating amount of the anode is 30mg/cm 2 ~60mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Then drying and rolling, and preparing the positive electrode, the diaphragm and the negative electrode together to prepare a lithium ion battery cell; the prepared concentrated salt electrolyte is added into a battery cell, and after sealing and standing, the battery can be charged. The prepared solid-state battery not only has excellent safety, but also can be compared with the existing lithium ion battery adopting the conventional electrolyte in terms of electrical performance.
Description
Technical Field
The invention belongs to the technical field of chemical power supplies, and particularly relates to a preparation method of a solid-state battery.
Background
The lithium ion/lithium battery is one of the most widely applied batteries at present, and has the advantages of high specific energy, high specific power, good low-temperature performance, long service life, no memory effect and the like.
The traditional lithium ion battery adopts inflammable organic electrolyte, and when the battery is used, the battery is at risk of fire explosion if accidents happen to the inside and the outside of the battery. To cope with this problem, it is an effective means to employ a nonflammable solid electrolyte. The concentrated salt electrolyte (liquid state) is easy to prepare, has good thermal stability and is nonflammable, and belongs to the category of quasi-solid electrolyte. Compared with the all-solid electrolyte, the concentrated salt electrolyte used for the lithium ion battery can be used without changing the existing production test equipment, and has high production efficiency and low cost. However, the viscosity of the concentrated salt electrolyte is high, the wettability of the counter electrode, especially the electrode with large coating amount is poor, so that the capacity of the battery is lower than the theoretical capacity of the battery core, the performance cannot be fully exerted, and the application of the concentrated salt electrolyte in the lithium ion/lithium battery is limited.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a preparation method of a solid-state battery, wherein polymer components in an anode can actively absorb concentrated salt electrolyte, so that the polarization phenomenon of the battery in the charge and discharge processes is effectively reduced, the battery core capacity can be fully exerted, and the prepared solid-state battery not only has excellent safety, but also can be compared with the existing lithium ion battery adopting conventional electrolyte in the aspect of electrical performance.
In order to achieve the above object, the technical scheme of the present invention is as follows:
a method of manufacturing a solid-state battery, the method comprising the steps of:
s1, adding a solvent into a homogenizing container, wherein the amount of the solvent used for preparing the slurry is 50-500 wt% of the solid content of the slurry; adding adhesive, wherein the total amount of the adhesive in the slurry is 0.1-30wt% of the solid content of the slurry; after fully stirring and dissolving, adding a conductive agent, wherein the conductive agent accounts for 0.05-20wt% of the solid content of the slurry; adding the anode active material powder after uniformly stirring, wherein the anode active material powder accounts for 50-99.85 wt% of the solid content of the slurry;
s2, coating the uniformly stirred slurry on an aluminum foil, wherein the coating amount of the anode is 30mg/cm 2 ~60mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Then drying at 100 ℃, rolling to form a positive electrode, and preparing a lithium ion battery cell together with a diaphragm and a negative electrode;
s3, adding a solvent and lithium salt into the container to prepare a concentrated salt electrolyte;
and S4, adding the prepared concentrated salt electrolyte into a battery cell, sealing and standing, and then charging the battery.
Furthermore, PVDF-HFP and P (MV-MA) are selected as adhesives for preparing the positive electrode in S1.
Further, the solvent in S1 includes, but is not limited to, one or both of NMP, DMSO, DMF.
Further, the conductive agent in S1 includes, but is not limited to, one or two of SP, VGCF, CNT and graphene.
Further, the positive electrode active material powder in S1 includes, but is not limited to, liCoO 2 、NCA、NCM、LiFePO 4 One or two of the following.
Further, the concentration of the concentrated salt electrolyte in S3 is 3.5mol/L to 6mol/L.
Further, the lithium salt used in S3 includes, but is not limited to, one or both of LiFSI and LiTFSI; the solvents used include, but are not limited to, one or more of DMC, DEC, EMC, EC, FEC.
The invention has the advantages and positive effects that:
1. the PVDF-HFP material adopted by the invention is widely used for gel electrolyte, and PVDF is not easy to be infiltrated by concentrated salt electrolyte due to higher crystallinity, but after the PVDF is copolymerized with HFP, the crystallinity is greatly reduced, and the wettability of the concentrated salt electrolyte is obviously improved; meanwhile, PVDF-HFP presents a porous structure after being dried, so that a small amount of concentrated salt electrolyte can be stored;
2. the P (MV-MA) material adopted by the invention has excellent wettability to concentrated salt electrolyte, and the coating amount is 30mg/cm 2 ~60mg/cm 2 The thick positive electrode can strengthen the absorption of polymer components in the positive electrode to the concentrated salt electrolyte;
3. the PVDF-HFP adopted by the invention is similar to PVDF in bonding capability, and can be used as an adhesive at the same time without adding other adhesives;
4. the PVDF-HFP and P (MV-MA) adopted by the invention have good oxidation resistance, can not be oxidized when the battery is charged, and have stable long-term use property.
5. The polymer component in the positive electrode can actively absorb the concentrated salt electrolyte, so that the polarization phenomenon of the battery in the charge and discharge process is effectively reduced, the battery core capacity can be fully exerted, the prepared solid-state battery not only has excellent safety, but also can be compared with the existing lithium ion battery adopting the conventional electrolyte in the aspect of electrical performance.
Detailed Description
For a further understanding of the invention, its features and advantages, the following examples are set forth to illustrate, but are not limited to, the following examples:
the invention relates to a preparation method of a solid-state battery, which comprises the following specific steps:
s1, adding a solvent into a homogenizing container, wherein the amount of the solvent used for preparing the slurry is 50-500 wt% of the solid content of the slurry; adding adhesive, wherein the total amount of the adhesive in the slurry is 0.1-30wt% of the solid content of the slurry; after fully stirring and dissolving, adding a conductive agent, wherein the conductive agent accounts for 0.05-20wt% of the solid content of the slurry; adding the anode active material powder after uniformly stirring, wherein the anode active material powder accounts for 50-99.85 wt% of the solid content of the slurry;
s2, coating the uniformly stirred slurry on an aluminum foil, wherein the coating amount of the anode is 30mg/cm 2 ~60mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Then drying at 100 ℃, rolling to form a positive electrode, and preparing a lithium ion battery cell together with a diaphragm and a negative electrode;
s3, adding a solvent and lithium salt into the container to prepare a concentrated salt electrolyte;
and S4, adding the prepared concentrated salt electrolyte into a battery cell, sealing and standing for 48 hours, and then charging the battery.
The preparation of the positive electrode in S1 adopts PVDF-HFP (polyvinylidene fluoride-hexafluoropropylene copolymer) and P (MV-MA) (polymethyl vinyl ether-maleic anhydride copolymer) as adhesives;
solvents in S1 include, but are not limited to, one or two of NMP (N-methylpyrrolidone), DMSO (dimethyl sulfoxide), DMF (dimethylformamide);
the conductive agent in S1 includes, but is not limited to, one or two of SP (conductive carbon black), VGCF (conductive carbon fiber), CNT (carbon nanotube), graphene;
the positive electrode active material powder in S1 is not limited to LiCoO 2 (lithium cobalt oxide), NCA (lithium nickel cobalt aluminate), NCM (lithium nickel cobalt manganate), liFePO 4 One or two of (lithium iron phosphate).
The concentration of the concentrated salt electrolyte in the S3 is 3.5mol/L to 6mol/L, the lithium salt used comprises one or two of LiFSI and LiTFSI, and the solvent used comprises one or more of DMC (dimethyl carbonate), DEC (diethyl carbonate), EMC (methyl ethyl carbonate), EC (ethylene carbonate) and FEC (fluoroethylene carbonate).
The invention is illustrated in detail below by means of 4 examples:
example 1:
s1, adding 5000g of NMP solvent into a homogenizing container; 200g of PVDF-HFP and 100g P (MV-MA) powder are added; after fully stirring and dissolving, 100g of SP and 100g of VGCF are added; after stirring, 500g LiCoO was added 2 A powder;
s2, after stirring uniformly, coating the slurry on an aluminum foil with the coating amount of 30mg/cm, and then drying at 100 ℃ and then rolling. The prepared positive electrode is matched with a diaphragm and a negative electrode to prepare a lithium ion battery cell;
s3, sequentially adding 45g of DMC, 1.32g of EC and 93.5g of LiFSI into a container, and uniformly stirring to form a concentrated salt electrolyte with the concentration of 6.0 mol/L;
and S4, adding the prepared concentrated salt electrolyte into a battery cell, sealing and standing for 48 hours, and then charging the battery.
The theoretical capacity of the prepared battery cell is 10.5Ah; the test battery A adopts the battery core and the concentrated salt electrolyte prepared by the scheme of the example 1, and the battery capacity is 10.45Ah; to verify the effect, we produced the following two comparative cells simultaneously:
the comparative battery (1) adopts the same cell as the test battery A, the electrolyte uses the conventional electrolyte, and the discharge capacity of the comparative battery (1) is 10.47Ah after test, which is basically the same as the test battery A.
The positive electrode used in comparative cell (2) was identical to the positive electrode prepared in the example 1 scheme, except that PVDF-HFP and P (MV-MA) binders were replaced with PVDF, and the other preparation parameters of the cell were identical. Comparative cell (2) the concentrated salt electrolyte prepared by the procedure of example 1 was used with a cell capacity of 9.07Ah.
By comparison, PVDF-HFP and P (MV-MA) adopted in the positive electrode can be better infiltrated by concentrated salt electrolyte, so that all capacities of the battery cells are exerted.
Example 2:
s1, adding 500g of DMSO solvent into a homogenizing container; 0.5g PVDF-HFP and 0.5g P (MV-MA) powder were added; after fully stirring and dissolving, adding 0.5g of CNT; after stirring evenly, 998.5g of NCA powder is added;
s2, after stirring uniformly, coating the slurry on an aluminum foil with the coating amount of 60mg/cm, and then drying at 100 ℃ and then rolling; the prepared positive electrode is matched with a diaphragm and a negative electrode to prepare a lithium ion battery cell;
s3, sequentially adding 107g of EMC, 2.5g of FEC and 93.5g of LiFSI into the container, and uniformly stirring to form a concentrated salt electrolyte with the concentration of 3.5 mol/L;
and S4, adding the prepared concentrated salt electrolyte into the battery, sealing and standing for 48 hours, and then charging the battery.
The theoretical capacity of the prepared battery cell is 11.8Ah; the battery B adopts the battery core and the concentrated salt electrolyte prepared by the scheme of the example 2, and the battery capacity is 11.78Ah; to verify the effect, we produced the following two comparative cells simultaneously:
the comparative battery (3) adopts the same battery core as the test battery B, the electrolyte uses the conventional electrolyte, and the discharge capacity of the comparative battery (3) is 11.77Ah and is basically the same as the test battery B after test;
the positive electrode used in comparative cell (4) was identical to the positive electrode prepared in the example 2 scheme, except that PVDF-HFP and P (MV-MA) were replaced with PVDF, and the other parameters of the cell preparation were the same. Comparative cell (4) the concentrated salt electrolyte prepared using the protocol of example 2 was used with a cell capacity of 9.94Ah.
By comparison, PVDF-HFP and P (MV-MA) adopted in the positive electrode can be better infiltrated by concentrated salt electrolyte, so that all capacities of the battery cells are exerted.
Example 3:
s1, adding 800g of DMF and 200g of NMP into a homogenizing container; a further 40g of PVDF-HFP and 10g P (MV-MA) powder are added; filling materialAfter being stirred and dissolved, 29.9g of SP and 0.1g of graphene are added; after stirring uniformly, 320g of NCM and 600g of LiFePO are added 4 A powder;
s2, after stirring uniformly, coating the slurry on an aluminum foil with the coating amount of 40mg/cm, and then drying at 100 ℃ and then rolling; the prepared positive electrode is matched with a diaphragm and a negative electrode to prepare a lithium ion battery cell;
s3, sequentially adding 125g of DEC, 2.12g of FEC, 1.1g of EC and 143.5g of LiTFSI into a container, and uniformly stirring to form 4.0mol/L of concentrated salt electrolyte;
and S4, adding the prepared concentrated salt electrolyte into the battery, sealing and standing for 48 hours, and then charging the battery.
The prepared battery cell theory capacity is 11.0Ah, the test battery C adopts the battery cell prepared by the scheme of the example 3 and the concentrated salt electrolyte, and the battery capacity is 10.98Ah; to verify the effect, we made two comparative cells at the same time.
The comparative battery (5) adopts the same battery core as the test battery C, the electrolyte uses the conventional electrolyte, and the discharge capacity of the comparative battery (5) is 11.01Ah after test, which is basically the same as the test battery C.
The positive electrode used in comparative cell (6) was identical to the positive electrode prepared in the example 3 scheme, except that PVDF-HFP and P (MV-MA) were replaced with PVDF, and the other parameters of the cell preparation were the same. Comparative cell (6) the concentrated salt electrolyte prepared using the protocol of example 3 was used with a cell capacity of 10.14Ah.
By comparison, PVDF-HFP and P (MV-MA) adopted in the positive electrode can be better infiltrated by concentrated salt electrolyte, so that all capacities of the battery cells are exerted.
Example 4:
s1, adding 1200g of NMP into a homogenizing container, and adding 20g of PVDF-HFP and 60g P (MV-MA) powder; after sufficiently stirring and dissolving, 0.05g of CNT and 0.95g of graphene were further added. After stirring evenly, 919g LiFePO is added 4 A powder;
s2, after stirring uniformly, coating the slurry on an aluminum foil with the coating amount of 55mg/cm, and then drying at 100 ℃ and then rolling; the prepared positive electrode, the diaphragm and the negative electrode are matched to prepare the lithium ion battery cell.
S3, sequentially adding 114g of EMC, 2.2g of EC, 93.5g of LiFSI and 28.7LiTFSI into the container, and uniformly stirring to form 4.5mol/L of concentrated salt electrolyte;
and S4, adding the prepared concentrated salt electrolyte into the battery, sealing and standing for 48 hours, and then charging the battery.
The prepared battery cell theory capacity is 9.50Ah, and the battery capacity of the test battery D is 9.46Ah by adopting the battery cell prepared by the scheme of the example 4 and the concentrated salt electrolyte; to verify the effect, we made two comparative cells at the same time.
The comparative battery (7) adopts the same cell as the test battery D, and the electrolyte uses a conventional electrolyte, and the discharge capacity of the comparative battery (7) is 9.45Ah after test, which is basically the same as the test battery D.
The positive electrode used in comparative cell (8) was identical to the positive electrode prepared in the example 4 scheme, except that PVDF-HFP and P (MV-MA) were replaced with PVDF, and the other parameters of the cell preparation were the same. Comparative cell (8) the concentrated salt electrolyte prepared using the protocol of example 4, cell capacity 8.29Ah.
By comparison, PVDF-HFP and P (MV-MA) adopted in the positive electrode can be better infiltrated by concentrated salt electrolyte, so that all capacities of the battery cells are exerted.
The embodiments described herein are only some, not all, embodiments of the invention. Based on the explanation and guidance of the above description, those skilled in the art can make alterations, improvements, substitutions, etc. to the embodiments based on the present invention and the examples, but all other examples obtained without making innovative research are included in the protection scope of the present invention.
Claims (5)
1. A method of manufacturing a solid-state battery, the method comprising the steps of:
s1, adding a solvent into a homogenizing container, wherein the amount of the solvent used for preparing the slurry is 50-500 wt% of the solid content in the slurry; adding an adhesive PVDF-HFP and a polymethyl vinyl ether-maleic anhydride copolymer, wherein the total amount of the adhesive in the slurry is 0.1-30wt% of the solid content in the slurry; after fully stirring and dissolving, adding a conductive agent, wherein the conductive agent accounts for 0.05-20wt% of the solid content in the slurry; adding the anode active material powder after uniformly stirring, wherein the anode active material powder accounts for 50-99.85 wt% of the solid content in the slurry;
s2, coating the uniformly stirred slurry on an aluminum foil, wherein the coating amount of the anode is 30mg/cm 2 ~60mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Then drying at 100 ℃, rolling to form a positive electrode, and preparing a lithium ion battery cell together with a diaphragm and a negative electrode;
s3, adding a solvent and lithium salt into the container to prepare a concentrated salt electrolyte; the concentration of the concentrated salt electrolyte is 3.5mol/L to 6mol/L;
and S4, adding the prepared concentrated salt electrolyte into a battery cell, sealing and standing, and then charging the battery.
2. The method of manufacturing a solid-state battery according to claim 1, wherein the solvent in S1 includes one or both of NMP, DMSO, DMF.
3. The method for manufacturing a solid-state battery according to claim 1, wherein the conductive agent in S1 includes one or both of SP, VGCF, CNT and graphene.
4. The method for producing a solid-state battery according to claim 1, wherein the positive electrode active material powder in S1 comprises LiCoO 2 Lithium nickel cobalt aluminate, lithium nickel cobalt manganate, liFePO 4 One or two of the following.
5. The method for producing a solid-state battery according to claim 1, wherein the lithium salt used in S3 comprises one or both of LiFSI and LiTFSI; the solvent used in S3 includes one or more of DMC, DEC, EMC, EC, FEC.
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