CN111799514A - Preparation method of positive plate or negative plate for solid-state battery, positive plate or negative plate for solid-state battery and solid-state battery - Google Patents
Preparation method of positive plate or negative plate for solid-state battery, positive plate or negative plate for solid-state battery and solid-state battery Download PDFInfo
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- 229910009290 Li2S-GeS2-P2S5 Inorganic materials 0.000 claims description 3
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- 229910006196 Li1+xAlxGe2−x(PO4)3 Inorganic materials 0.000 claims description 2
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- 229910006212 Li1+xAlxTi2−x(PO4)3 Inorganic materials 0.000 claims description 2
- 229910005317 Li14Zn(GeO4)4 Inorganic materials 0.000 claims description 2
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- 229910005833 GeO4 Inorganic materials 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a preparation method of a positive plate or a negative plate for a solid-state battery, the positive plate or the negative plate and the solid-state battery, wherein the preparation method comprises the following steps: putting inorganic solid electrolyte powder with lithium ion conductivity and an organic polymer electrolyte material into an organic solvent, and uniformly mixing; pre-dispersing the obtained composite electrolyte coating slurry; uniformly spraying the pre-dispersed composite electrolyte coating slurry on the positive plate or the negative plate by adopting an ultrasonic atomization spraying machine; and drying the pole piece sprayed with the composite electrolyte coating slurry to obtain the positive pole piece or the negative pole piece coated with the composite electrolyte layer. By adopting the method, the over-spraying can be avoided, the accurate liquid drop distribution is realized, the accurate micron-thick coating is formed, and the coating is thin, uniform and controllable; waste and air pollution caused by reverse spraying can be reduced, and cost is saved; the energy consumption is low, and atomizing efficiency is high, and is less to the restriction of atomizing liquid, and the thick liquids utilization ratio reaches more than 90%, can improve production efficiency greatly.
Description
Technical Field
The invention relates to the technical field of solid-state battery preparation, in particular to a preparation method of a positive plate or a negative plate for a solid-state battery, the positive plate or the negative plate for the solid-state battery and the solid-state battery.
Background
At present, the traditional slurry coating process of the lithium ion battery mainly adopts two types of roller coating transfer coating and extrusion coating. The roller coating transfer type coating utilizes the rotation of a coating roller to drive slurry, the slurry transfer amount is adjusted by adjusting the gap of a scraper, the slurry is transferred onto a base material by utilizing the rotation of a back roller or the coating roller, and the thickness of a coating layer is controlled according to the process requirement so as to meet the load requirement. The roller coating transfer type coating has poor coating precision, the consistency of a coating cannot be ensured, and slurry is exposed in air between rollers and has partial influence on the slurry property. The extrusion coating is characterized in that slurry is conveyed to a screw pump through a feeding system, then conveyed to an extrusion head, made into a liquid film through an extrusion mode, coated on a moving current collector, and dried to form a coating with uniform texture. Extrusion coating has high requirements on equipment precision, high requirements on maintenance and high requirements on the viscosity range of slurry, and a new gasket needs to be replaced when specifications are changed, so that the production efficiency is reduced.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide a preparation method of a positive plate or a negative plate for a solid-state battery, by adopting the preparation method, the thickness of a composite electrolyte layer sprayed on the positive plate or the negative plate can be accurately controlled, and the preparation method has the advantages of uniform coating, high slurry utilization rate, cost saving, low energy consumption and the like.
The second purpose of the invention is to provide a positive plate or a negative plate for a solid-state battery, wherein the composite electrolyte layer on the positive plate or the negative plate is thin, uniform and controllable.
A third object of the present invention is to provide a solid-state battery having advantages of high energy density and good product safety.
In order to achieve the first object, the invention provides the following technical scheme:
a preparation method of a positive plate or a negative plate for a solid-state battery comprises the following steps:
and 4, drying the pole piece sprayed with the composite electrolyte coating slurry to obtain the positive pole piece or the negative pole piece coated with the composite electrolyte layer. The drying temperature and time are determined according to the solvent, the temperature range is 40-80 ℃, and the time is 2-5 min.
By adopting the technical scheme, the ultrasonic frequency of atomization of the ultrasonic atomization spraying machine is controlled to be 30-130 kHz, the flow rate of matched carrier gas is controlled to be 1-5L/min, and the liquid inlet rate of a matched nozzle is controlled to be 1-10 mL/min, so that the slurry can be ensured to be uniformly and fully attached to the positive plate or the negative plate as much as possible, excessive spraying is avoided, accurate liquid drop distribution is realized, and a more uniform, thinner and more controllable film coating is formed; as the flow of the carrier gas is controlled to be 1-5L/min, the matched nozzle of the ultrasonic atomization spraying machine only needs the micro gas flow of the kilopascal level, so that splashing is hardly generated in the spraying process, the utilization rate of the slurry is also improved, the cost is saved, the pollution is reduced, and the production efficiency is improved. Preferably, the spraying distance between the matched spray head and the electrode plate to be sprayed is 20-50 mm.
Preferably, the particle size of the inorganic solid electrolyte powder is 0.5-1.0 μm, and the solid content of the obtained composite electrolyte coating slurry is 15-20 wt%.
The particle size of the inorganic solid electrolyte powder is preferably 0.5-1.0 mu m, so that the dispersibility of the powder is improved, the inorganic solid electrolyte material is uniformly distributed in the coating, and the energy density and the cycle performance of the solid battery are improved.
The solid content of the composite electrolyte coating slurry is preferably 15-20 wt%, so that the energy consumption is low and the utilization rate of the slurry is high. The traditional roll coating method is expected to have higher solid content, so that the raw material cost can be reduced, but a certain amount of slurry is required to circulate to roll the roll to realize coating, so that the utilization rate of the slurry is low.
Preferably, in the step 1, the mass ratio of the inorganic solid electrolyte powder to the organic polymer electrolyte material is (1-20): 1, the organic solvent is N, N-dimethylformamide, acetonitrile, N-methylpyrrolidone or xylene. Preferably, the mass ratio of the inorganic solid electrolyte powder to the organic polymer electrolyte material is (5-20): this is because, when the mass ratio of the inorganic solid electrolyte is increased (i.e., the mass ratio of the organic polymer electrolyte material is decreased), the internal resistance of the battery obtained by using the electrode sheet coated with the slurry becomes smaller, and conversely, the internal resistance of the battery becomes larger.
Preferably, the inorganic solid state electrolyte material having lithium ion conductivity is selected from one or more of a NASICON-type lithium ion inorganic solid state electrolyte material, a perovskite-type lithium ion inorganic solid state electrolyte material, a LISICON-type lithium ion inorganic solid state electrolyte material, a garnet-type lithium ion inorganic solid state electrolyte material, an inverse perovskite-type lithium ion inorganic solid state electrolyte material, and a sulfide-type lithium ion inorganic solid state electrolyte material.
Preferably, the NASICON type lithium ion inorganic solid state electrolyte material is selected from LiM1 2(PO4)3(M1＝Ti、Ge、Hf)、Li1+xAlxTi2-x(PO4)3(0.1<x<0.5, LATP system), Li1+xAlxGe2-x(PO4)3(0.1<x<0.5, LAGP system); the perovskite type lithium ion inorganic solid electrolyte material is selected from Li0.34La0.56TiO3、Li0.5La0.5TiO3Or a combination of the two; LISICON type lithiumThe ionic inorganic solid electrolyte material is Li14Zn(GeO4)4(ii) a The garnet type lithium ion inorganic solid electrolyte material is selected from Li5La3M2 2O12、Li6ALa2M2 2O12、Li5.5La3M2 1.75B0.25O12、Li7La3Zr2O12、Li7.06M3 3Y0.06Zr1.94O12Wherein M is2Represents Nb or Ta, A represents Ca, Sr or Ba, B represents In or Zr, M3Represents La, Nb or Ta; the general formula of the anti-perovskite type lithium ion inorganic solid electrolyte material is Li3-2xM4 xHalO, wherein x is more than or equal to 0 and less than or equal to 0.01, M4Represents Mg, Ca, Sr or Ba, Hal represents Cl or I; the sulfide type lithium ion inorganic solid electrolyte material is selected from Li2S-SiS2、Li2S-P2S5、Li2S-GeS2、Li2S-GeS2-P2S5、Li2S-SnS2-P2S5、Li2S-Al2S3-P2S5One or more of (a).
Preferably, in step 1, the organic polymer electrolyte material is one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, polyethylene oxide (Mw ═ 30 to 70 ten thousand), polypropylene oxide, polyvinylpyrrolidone, polyvinyl alcohol, polyimide, polyacrylic acid (Mw ═ 30 to 60 ten thousand), and ethylene-vinyl acetate copolymer.
Preferably, in the step 1, the mixing method is a mechanical stirring method or a high-energy ball milling method; wherein, the ball-material ratio in the high-energy ball milling method is 1: 2-1: 8, the rotating speed is 200-400 r/min, and the ball milling time is 5-20 hours.
Preferably, in the step 2, the pre-dispersion treatment is realized by mechanical stirring operation or ultrasonic dispersion operation; wherein the ultrasonic dispersion operation is realized by an ultrasonic cell crusher, the ultrasonic power is 50-100W, and the ultrasonic dispersion time is 1-10 min.
In order to achieve the second object, the invention provides the following technical scheme:
a positive plate or a negative plate for a solid-state battery is prepared by the preparation method.
Preferably, the thickness of the composite electrolyte layer coated on the positive plate or the negative plate is 1-10 μm.
In order to achieve the third object, the invention provides the following technical solutions:
the utility model provides a solid-state battery, includes electric core, electric core is formed according to the order equipment of negative pole piece, positive plate, negative pole piece, positive plate … … negative pole piece by a plurality of negative pole pieces, positive plate, negative pole piece, positive plate adopt aforementioned solid-state battery respectively with negative pole piece or positive plate.
In conclusion, the invention has the following beneficial effects:
1. in the preparation process of the composite electrolyte layer provided by the invention, through accurately controlling each process parameter of ultrasonic atomization, over-spraying can be avoided, accurate liquid drop distribution is realized, and an accurate micron-thick coating is formed;
2. waste and air pollution caused by back spray can be reduced by ultrasonic atomization spraying, and cost is saved;
3. the ultrasonic atomization spraying energy consumption is low, the atomization efficiency is high, the limit on atomized liquid is small, the utilization rate of the slurry is up to more than 90%, and the production efficiency can be greatly improved;
4. by adopting the preparation method provided by the invention, the composite electrolyte layer on the positive plate or the negative plate is thin, uniform and controllable.
Drawings
FIG. 1 is a test chart of the peel strength of a negative electrode sheet of example 1;
FIG. 2 is a test chart of the peel strength of the negative electrode sheet of example 3;
FIG. 3 is a test chart of the peel strength of the negative electrode sheet of example 6;
FIG. 4 is a test chart of peel strength of negative electrode sheets of example 13;
FIG. 5 is a test chart of the peel strength of the negative electrode sheet of example 15;
FIG. 6 is a test chart of the peel strength of the negative electrode sheet of example 17;
FIG. 7 is a test chart of the peel strength of the negative electrode sheet of example 20;
FIG. 8 is a test chart of the peel strength of a negative electrode sheet of example 29;
fig. 9 is a test chart of the peel strength of the negative electrode sheet of example 30.
Detailed Description
The reagents and equipment used in the following examples are commercially available.
Wherein, the ultrasonic atomization coating machine is manufactured by Beijing Oriental Jinrong ultrasonic electric appliance Co, Ltd, and the model is UC360 c.
The high-energy ball mill is manufactured by Nanda instruments of Nanjing, and has the model number of QM-3SP 2.
The ultrasonic cell disruptor was manufactured by Ningbo Xinzhi Biotech Co., Ltd, model number SCIENTZ-IID.
Example 1
The preparation method of the negative electrode sheet for the solid-state battery provided in this embodiment specifically includes the following steps:
And 4, drying the negative plate sprayed with the composite electrolyte layer at 60 ℃ for 3min to obtain the negative plate with the composite electrolyte layer.
Example 2
The preparation method of the negative electrode plate for the solid-state battery provided in this embodiment is mainly the same as that in embodiment 1, except that in the spraying process in step 2, the ultrasonic frequency of the atomization performed by the ultrasonic atomization spraying machine is 60 Hz.
Example 3
The preparation method of the negative electrode plate for the solid-state battery provided in this embodiment is mainly the same as that in embodiment 1, except that in the spraying process in step 2, the ultrasonic frequency of the atomization performed by the ultrasonic atomization spraying machine is 90 Hz.
Example 4
The preparation method of the negative electrode plate for the solid-state battery provided in this embodiment is mainly the same as that in embodiment 1, except that in the spraying process in step 2, the ultrasonic frequency of the atomization performed by the ultrasonic atomization spraying machine is 130 Hz.
Example 5
The method for preparing the negative electrode plate for the solid-state battery provided in this embodiment is mainly the same as that in embodiment 2, except that in the spraying process in step 2, the liquid inlet rate of the matched nozzle is 2 mL/min.
Example 6
The preparation method of the negative electrode plate for the solid-state battery provided in this embodiment is mainly the same as that in embodiment 2, except that in the spraying process in step 2, the liquid inlet rate of the matched nozzle is 3 mL/min.
Example 7
The preparation method of the negative electrode plate for the solid-state battery provided in this embodiment is mainly the same as that in embodiment 2, except that in the spraying process in step 2, the liquid inlet rate of the matched nozzle is 5 mL/min.
Example 8
The preparation method of the negative electrode plate for the solid-state battery provided in this embodiment is mainly the same as that in embodiment 2, except that in the spraying process in step 2, the liquid inlet rate of the matched nozzle is 7 mL/min.
Example 9
The preparation method of the negative electrode plate for the solid-state battery provided in this embodiment is mainly the same as that in embodiment 2, except that in the spraying process in step 2, the liquid inlet rate of the matched nozzle is 10 mL/min.
Example 10
The method for preparing the negative electrode plate for the solid-state battery provided in this embodiment is mainly the same as that in embodiment 6, except that in the spraying process in step 2, the rate of the matched carrier gas (compressed nitrogen) is 2L/min.
Example 11
The method for preparing the negative electrode plate for the solid-state battery provided in this embodiment is mainly the same as that in embodiment 6, except that in the spraying process in step 2, the rate of the matched carrier gas (compressed nitrogen) is 3L/min.
Example 12
The method for preparing the negative electrode plate for the solid-state battery provided in this embodiment is mainly the same as that in embodiment 6, except that in the spraying process in step 2, the rate of the matched carrier gas (compressed nitrogen) is 5L/min.
Example 13
The method for preparing the negative electrode plate for the solid-state battery provided in this example is mainly the same as example 11, except that in the spraying process in step 2, the spraying distance is 30 mm.
Example 14
The method for preparing the negative electrode plate for the solid-state battery provided in this example is mainly the same as example 11, except that in the spraying process in step 2, the spraying distance is 40 mm.
Example 15 (Note: examples 15 to 16 for examining the influence of the particle size of the powder)
The method for preparing the negative electrode sheet for the solid-state battery provided in this example is mainly the same as example 13, except that in step 1, the garnet-type lithium ion inorganic solid-state electrolyte material Li7La3Zr2O12The particle size of the powder was 0.7. mu.m.
Example 16
The method for preparing the negative electrode sheet for the solid-state battery provided in this example is mainly the same as example 13, except that in step 1, the garnet-type lithium ion inorganic solid-state electrolyte material Li7La3Zr2O12The particle size of the powder was 1.0. mu.m.
Example 17
The method for preparing the negative electrode sheet for the solid-state battery provided in this example is mainly the same as example 15, except that in step 1, the garnet-type lithium ion inorganic solid-state electrolyte material Li7La3Zr2O12The mass of the powder is 15kg, and the mass ratio of the organic polymer electrolyte material polyvinylidene fluoride powder is 1 kg.
Example 18
The method for preparing the negative electrode sheet for the solid-state battery provided in this example is mainly the same as example 15, except that in step 1, the garnet-type lithium ion inorganic solid-state electrolyte material Li7La3Zr2O12The mass of the powder is 10kg, and the mass of the polyvinylidene fluoride powder serving as the organic polymer electrolyte material is 1 kg.
Example 19
The method for preparing the negative electrode sheet for the solid-state battery provided in this example is mainly the same as example 15, except that in step 1, the garnet-type lithium ion inorganic solid-state electrolyte material Li7La3Zr2O12The mass of the powder is 5kg, and the mass of the polyvinylidene fluoride powder serving as the organic polymer electrolyte material is 1 kg.
Example 20
The method for preparing the negative electrode plate for the solid-state battery provided in this example is mainly the same as example 17, except that, in step 1, the amount of the organic solvent N, N-dimethylformamide is 59kg, and the solid content of the prepared composite electrolyte slurry is 20 wt%.
Example 21
The method for preparing the negative electrode plate for the solid-state battery provided in this example is mainly the same as example 17, except that in step 1, the amount of the organic solvent N, N-dimethylformamide is 84kg, and the solid content of the prepared composite electrolyte slurry is 15 wt%.
Example 22
The method for preparing a positive electrode plate for a solid-state battery according to this embodiment is mainly the same as in embodiment 20, except that, in step 1, an anti-perovskite lithium ion inorganic solid-state electrolyte material Li is selected as the inorganic solid-state electrolyte material3OCl, wherein the organic polymer electrolyte material is polyoxyethylene, and the organic solvent is acetonitrile.
Example 23
The method for preparing a positive electrode plate for a solid-state battery provided in this example is mainly the same as example 20, except that in step 1, an inorganic solid-state electrolyte material is an anti-perovskite lithium ion inorganic solid-state electrolyte material licooi, an organic polymer electrolyte material is polyethylene oxide, and an organic solvent is acetonitrile.
Example 24
The method for preparing a negative electrode sheet for a solid-state battery according to this example is mainly the same as in example 20, except that in step 1, the inorganic solid-state electrolyte material is NASICON-type inorganic solid-state electrolyte material Li1.4Al0.4Ti1.6(PO4)3The organic polymer electrolyte material is polyvinylidene fluoride-hexafluoropropylene copolymer.
Example 25
The method for preparing a negative electrode sheet for a solid-state battery according to this example is mainly the same as in example 20, except that in step 1, the inorganic solid-state electrolyte material is NASICON-type inorganic solid-state electrolyte material Li1.5Al0.5Ge1.5(PO4)3The organic polymer electrolyte material is polyethylene oxide, and the organic solvent is acetonitrile.
Example 26
The method for preparing the negative electrode plate for the solid-state battery provided in this embodiment is mainly the same as that in embodiment 20, except that in step 1, the inorganic solid-state electrolyte material is perovskite-type lithium ion inorganic solid-state electrolyte material Li0.34La0.56TiO3The organic polymer electrolyte material is polyoxyethylene, and the organic solvent is acetonitrile.
Example 27
The method for preparing the negative electrode plate for the solid-state battery provided in this embodiment is mainly the same as that in embodiment 20, except that, in step 1, the inorganic solid-state electrolyte material is Li, which is a LISICON-type lithium ion inorganic solid-state electrolyte material14Zn(GeO4)4The organic polymer electrolyte material is polyvinylidene fluoride, and the organic solvent is N-methyl pyrrolidone.
Example 28
The method for preparing a negative electrode sheet for a solid-state battery according to this embodiment is mainly the same as in embodiment 20, except that, in step 1, the inorganic solid-state electrolyte material is a sulfide-type inorganic solid-state electrolyte material Li2S-GeS2-P2S5The organic polymer electrolyte material is polyoxyethylene, and the organic solvent is acetonitrile.
Example 29
The method for preparing the negative electrode plate for the solid-state battery provided in this embodiment is mainly the same as in embodiment 20, except that, in step 1, a high-energy ball mill is used for mixing, the high-energy ball mill is used for 5 hours, the rotating speed is 300 rpm, the ball-to-material ratio is 1:4, and zirconia balls are used.
Example 30
In the preparation method of the negative electrode sheet for the solid-state battery provided in this embodiment, on the basis of embodiment 29, in step 2, an ultrasonic cell crusher is used for pre-dispersion, the ultrasonic power is 80W, and the ultrasonic time is 3 min.
Comparative example 1
The negative plate was prepared using the composite electrolyte slurry of example 1 except that in step 3, the feed rate of the mating nozzle of the ultrasonic atomization coating machine was controlled to be 0.5 mL/min.
Comparative example 2
The negative plate was prepared using the composite electrolyte slurry of example 1 except that in step 3, the feed rate of the mating nozzle of the ultrasonic atomization coating machine was controlled to be 15 mL/min.
Comparative example 3
The composite electrolyte slurry of example 1 was used to prepare a negative electrode sheet, except that in step 3, the carrier gas rate associated with the ultrasonic atomizing spray coater was 0.5L/min.
Comparative example 4
The composite electrolyte slurry of example 1 was used to prepare a negative electrode sheet, except that in step 3, the carrier gas rate associated with the ultrasonic atomizing spray coater was 6L/min.
Comparative example 5
Comparative example 5 coating of the composite electrolyte slurry was performed using a roll coating transfer coating process to produce a negative electrode sheet coated with a composite electrolyte layer.
The composition of the composite electrolyte slurry is the same as that of the composite electrolyte slurry in the embodiment 1, and the technological parameters of the roller coating transfer type coating are as follows: a 250-mesh coating roller, the coating speed is 1m/s, and the coating speed ratio is 1.3.
Performance testing
(1) Detecting the thickness of the coating: taking the pole pieces of examples 1-30 and comparative examples 1-5, cutting 10 square samples with side length of 2mm for each pole piece, selecting 6 different positions, measuring the coating thickness by a thickness gauge, calculating the average thickness of the coating, and evaluating the uniformity of the coating by using CoV (i.e. relative standard deviation) (generally requiring less than 5%), and the results are shown in Table I.
In connection with Table one, the analysis is as follows:
it can be seen from comparative examples 1 to 4 that the average thickness of the coating layer did not vary much as the ultrasonic frequency increased, indicating that the ultrasonic frequency had little effect on the average thickness of the coating layer, but that the coating layer had relatively excellent uniformity when the ultrasonic frequency was 60kHz (see example 2).
As can be seen from comparison of examples 1 and 5 to 9, the coating thickness increased as the shower head feed rate increased when the carrier gas rate was fixed, but the coating had relatively excellent uniformity when the shower head feed rate was 3L/min (see example 6).
By combining the examples 2, 5-12 and the comparative examples 1, 2, 3, 4, it can be seen that the average thickness of the coating is smaller when the carrier gas rate and the nozzle liquid inlet rate are lower; the influence of the shower head feed rate on the average thickness of the coating was large relative to the carrier gas rate, and when the carrier gas rate was also 3L/min (see example 11), the coating thickness was 4.5 μm, the thickness was appropriate, and relatively excellent uniformity was exhibited. However, when the liquid inlet rate of the spray head is too low (see comparative example 1), the slurry adhesion efficiency is low, the coating is not thick enough, and when the liquid inlet rate of the spray head is too high (see comparative example 2), the slurry is easy to splash during coating, so that the slurry is wasted, and the coating uniformity is poor.
It can be seen from comparative examples 11, 13 and 14 that the average thickness of the coating is slightly affected by the spraying distance under the condition of the same carrier gas velocity and the same shower head liquid inlet velocity, but the spraying distance is relatively smaller, such as 20mm in example 11, and the coating has relatively excellent uniformity.
It can be seen from comparison of examples 13, 15 and 16 and examples 17 to 28 that the average thickness of the coating layer does not substantially change when the carrier gas rate, the head feed rate and the spraying distance are fixed and other parameters are changed. However, the particle size of the inorganic solid electrolyte material has a certain influence on the uniformity of the coating, and the uniformity of the coating is not good enough when the particle size is small (0.5 μm) or large (1.0 μm), and the uniformity of the coating is relatively good when the particle size is 0.7 μm (see example 15); the mass ratio of the inorganic solid electrolyte material to the organic polymer electrolyte material also has a certain influence on the uniformity of the coating, and when the mass ratio of the organic polymer electrolyte material is small and the mass ratio of the inorganic solid electrolyte material is large, the uniformity of the coating is not good enough but the internal resistance of the battery is small (see example 17), and conversely, the uniformity of the coating is good but the internal resistance of the battery is large (see example 19).
As can be seen from comparison of examples 13, 20 and 21, the coating uniformity is affected by the solid content being either lower (e.g., 15% in example 21) or higher (e.g., 25% in example 13); and the coating thickness is greatly influenced when the solid content is small (15%), and the coating has relatively excellent uniformity when the solid content is 20% (see example 20).
As can be seen from comparison of examples 29 and 30, the inorganic solid electrolyte material and the organic polymer electrolyte material are more uniformly dispersed by high-energy grinding, and the uniformity of the thickness of the coating is improved; the uniformity of the coating thickness is further improved after the slurry is subjected to the ultrasonic pre-dispersion treatment on the basis of the example 29.
(2) Adhesion (peel strength) test: for the pole piece samples of representative examples 1, 3, 6, 13, 15, 17, 20, 29, and 30 of the present application, a 3M adhesive tape was respectively adhered to the surface of the pole piece, a sample with a width of 10mm was cut, the 3M adhesive tape was peeled off at an angle of 180 ° and at a speed of 50mm/min on a tensile testing machine, and the peeling force with which the coating was peeled off was measured, and the peeling force divided by the sample width was the peeling strength, and the results of the detection are shown in fig. 1-9 and table two.
Watch two
| Examples | Peel strength (N/m) |
| 1 | 48 |
| 3 | 56 |
| 6 | 59 |
| 13 | 65 |
| 15 | 58 |
| 17 | 68 |
| 20 | 60 |
| 29 | 68 |
| 30 | 72 |
As can be seen from fig. 1-9 and table two: as can be seen from comparison of examples 1, 3, 6, 13, 15, 17, and 20, the ultrasonic frequency, the liquid inlet rate, the spraying distance, the raw material mass ratio, and the solid content were adjusted to obtain a suitable coating thickness and to achieve better dispersibility of the coating; comparing examples 29 and 30, it can be seen that the inorganic solid electrolyte material and the organic polymer electrolyte material are dispersed more uniformly after the slurry is subjected to high-energy grinding and ultrasonic pre-dispersion treatment, and the peel strength of the coating is further improved.
(3) Detecting the energy density of the battery:
the cells of the solid-state batteries were assembled from the negative electrode sheets of examples 1, 2, 5, 6, 9, 10, 12, 13, 15, 16, 17, 18, 19, 20, 21, and 30, which are representative negative electrode sheets of the present invention, the negative electrode sheets of comparative examples 1, 2, and 5, and the positive electrode sheet of example 22, which is a representative positive electrode sheet, respectively, and the sizes and specifications of the resulting solid-state batteries were the same. The method comprises the following specific steps: the negative electrode sheet or the positive electrode sheet of example 22 was first cut into desired dimensions, and then laminated in the order of the negative electrode sheet, the positive electrode sheet, the negative electrode sheet, and the positive electrode sheet … … (total of 12 negative electrode sheets and 11 positive electrode sheets, where the number of the electrode sheets is merely exemplary and not limiting to the present invention), and then subjected to tab welding, packaging, and pre-charging in a conventional manner to form a solid-state battery.
The solid-state battery obtained above was subjected to energy density detection by the following method:
discharging at constant current of 1C to 3.0V, standing for 1h, charging at constant current of 1C, charging at constant voltage when battery voltage reaches 4.2V, and stopping charging when charging current decreases to 0.1A. According to the test results, an average discharge voltage and an energy density according to the weight of the active material of the electrode were obtained, and the results are shown in table two.
(4) And (3) detecting the cycle life: the cycle life of the solid-state battery prepared by the method is detected by a cycle test method (or a detection standard) specified in GB/T31484 or GB/T31486, and the detection results are listed in Table III.
Watch III
| Pole piece | Average discharge voltage/V | Energy Density/Wh/kg | Cycle life (times) |
| Example 1 | 3.78 | 219 | 850 |
| Example 2 | 3.67 | 218 | 880 |
| Example 5 | 3.79 | 216 | 980 |
| Example 6 | 3.76 | 213 | 1040 |
| Example 9 | 3.74 | 203 | 1120 |
| Example 10 | 3.78 | 212 | 1080 |
| Example 12 | 3.71 | 209 | 1110 |
| Example 13 | 3.79 | 212 | 1100 |
| Example 15 | 3.69 | 213 | 1050 |
| Example 16 | 3.78 | 211 | 1020 |
| Example 17 | 3.76 | 212 | 1130 |
| Example 18 | 3.69 | 214 | 1020 |
| Example 19 | 3.78 | 215 | 980 |
| Example 20 | 3.79 | 211 | 1150 |
| Example 21 | 3.71 | 215 | 1130 |
| Example 30 | 3.67 | 217 | 1200 |
| Comparative example 1 | 3.70 | 221 | 650 |
| Comparative example 2 | 3.72 | 197 | 1250 |
| Comparative example 5 | 3.76 | 203 | 950 |
And (4) analyzing results: as can be seen from the table III, the coating prepared by ultrasonic atomization spraying has good uniformity, the uniformity CoV (relative standard deviation) is less than 5%, and when the average thickness of the coating is about 4-5mm, the corresponding solid-state battery has higher energy density, better cycle performance and wide application prospect and advantages.
The existing mode of coating the slurry by adopting a roll coating method needs to ensure that the slurry is fully attached to a roll to be coated well, the residual slurry after coating is finished cannot be reused, and part of slurry is exposed in the environment in the coating process to influence the coating performance. This application adopts the mode of ultrasonic atomization spraying, can obtain the even positive plate or negative plate of coating thickness, and gained solid-state battery energy density is high, and the cyclicity can be strong, and its performance reaches and is superior to prior art even, but simultaneously, for the mode that adopts roller coating method coating thick liquids now, this application can make full use of the thick liquids of preparing, reduce cost, and relatively wide range to the requirement of thick liquids viscosity or solid content, easily realization.
The above specific embodiments are merely illustrative of the present invention, and are not restrictive, and those skilled in the art can modify the embodiments without inventive contribution as required after reading the present specification, but only fall within the scope of the claims of the present invention.
Claims (10)
1. A preparation method of a positive plate or a negative plate for a solid-state battery is characterized by comprising the following steps:
step 1, putting inorganic solid electrolyte powder with lithium ion conduction capability and an organic polymer electrolyte material into an organic solvent, and uniformly mixing to obtain composite electrolyte coating slurry; wherein the particle size of the inorganic solid electrolyte powder is 0.1-10 μm, and the solid content of the obtained composite electrolyte coating slurry is 10-35 wt%;
step 2, performing pre-dispersion treatment on the composite electrolyte coating slurry;
step 3, uniformly spraying the composite electrolyte coating slurry subjected to pre-dispersion treatment onto the positive plate or the negative plate by using an ultrasonic atomization spraying machine, wherein the ultrasonic frequency of atomization performed by using the ultrasonic atomization spraying machine is 30-130 kHz, the flow rate of matched carrier gas is 1-5L/min, and the liquid inlet rate of a matched spray head is 1-10 mL/min;
and 4, drying the pole piece sprayed with the composite electrolyte coating slurry to obtain the positive pole piece or the negative pole piece coated with the composite electrolyte layer.
2. The preparation method according to claim 1, wherein in the step 1, the mass ratio of the inorganic solid electrolyte powder to the organic polymer electrolyte material is (1-20): 1, the organic solvent is N, N-dimethylformamide, acetonitrile, N-methylpyrrolidone or xylene.
3. The production method according to claim 1, characterized in that the inorganic solid state electrolyte material having lithium ion conductivity is selected from one or more of a NASICON-type lithium ion inorganic solid state electrolyte material, a perovskite-type lithium ion inorganic solid state electrolyte material, a LISICON-type lithium ion inorganic solid state electrolyte material, a garnet-type lithium ion inorganic solid state electrolyte material, an anti-perovskite-type lithium ion inorganic solid state electrolyte material, and a sulfide-type lithium ion inorganic solid state electrolyte material.
4. The production method according to claim 3,
the NASICON type lithium ion inorganic solid electrolyte material is selected fromLiM1 2(PO4)3（M1=Ti、Ge、Hf）、Li1+xAlxTi2-x(PO4)3(0.1<x<0.5)、Li1+xAlxGe2-x(PO4)3(0.1<x<0.5) one or more of;
the perovskite type lithium ion inorganic solid electrolyte material is selected from Li0.34La0.56TiO3、Li0.5La0.5TiO3Or a combination of the two;
the LISICON type lithium ion inorganic solid electrolyte material is Li14Zn(GeO4)4；
The garnet type lithium ion inorganic solid electrolyte material is selected from Li5La3M2 2O12、Li6ALa2M2 2O12、Li5.5La3M2 1.75B0.25O12、Li7La3Zr2O12、Li7.06M3 3Y0.06Zr1.94O12Wherein M is2Represents Nb or Ta, A represents Ca, Sr or Ba, B represents In or Zr, M3Represents La, Nb or Ta;
the general formula of the trans-perovskite type lithium ion inorganic solid electrolyte material is Li3-2xM4 xHalO, wherein x is more than or equal to 0 and less than or equal to 0.01, M4Represents Mg, Ca, Sr or Ba, Hal represents Cl or I;
the sulfide type lithium ion inorganic solid electrolyte material is selected from Li2S-SiS2、Li2S-P2S5、Li2S-GeS2、Li2S-GeS2-P2S5、Li2S-SnS2-P2S5、Li2S-Al2S3-P2S5One or more of (a).
5. The method according to claim 1, wherein in step 1, the organic polymer electrolyte material is one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, polyethylene oxide, polypropylene oxide, polyvinylpyrrolidone, polyvinyl alcohol, polyimide, polyacrylic acid, and ethylene-vinyl acetate copolymer.
6. The method according to claim 1, wherein in the step 1, the mixing method is a mechanical stirring method or a high-energy ball milling method; wherein, the ball-material ratio in the high-energy ball milling method is 1: 2-1: 8, the rotating speed is 200-400 r/min, and the ball milling time is 5-20 hours.
7. The preparation method according to claim 1, wherein in step 2, the pre-dispersion treatment is carried out by a mechanical stirring operation or an ultrasonic dispersion operation; wherein the ultrasonic dispersion operation is realized by an ultrasonic cell crusher, the ultrasonic power is 50-100W, and the ultrasonic dispersion time is 1-10 min.
8. A positive electrode sheet or a negative electrode sheet for a solid-state battery, characterized in that the positive electrode sheet or the negative electrode sheet is produced by the production method according to any one of claims 1 to 10.
9. The positive or negative electrode sheet according to claim 8, wherein the thickness of the composite electrolyte layer applied to the positive or negative electrode sheet is 1 to 10 μm.
10. A solid-state battery, includes electric core, its characterized in that, electric core is assembled according to negative pole piece, positive plate, negative pole piece, positive plate … … negative pole piece's mode by a plurality of negative pole pieces, positive plate, negative pole piece, positive plate adopt claim 8 respectively negative pole piece or positive plate for solid-state battery.
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