CN113394463A - Sulfide-based solid electrolyte all-solid-state battery and preparation method thereof - Google Patents
Sulfide-based solid electrolyte all-solid-state battery and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- 238000000034 method Methods 0.000 claims abstract description 31
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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
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- 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
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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
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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 application relates to the field of solid-state batteries, in particular to a sulfide-based solid electrolyte all-solid-state battery and a preparation method thereof, wherein the preparation method of the sulfide-based solid electrolyte all-solid-state battery specifically comprises the following steps: s1, preparing a positive electrode ring and a negative electrode rod; s2, pressing the positive ring into the shell to be used as the positive pole of the battery; s3, coating the solid electrolyte membrane on the inner surface of the positive electrode ring and forming a membrane; s4, pressing a negative rod with a current collecting net into the inner wall of the solid electrolyte membrane to be used as a negative electrode of the battery; s5, further applying additional pressure which is larger than the pre-pressing pressure of the negative electrode to enable the positive electrode and the negative electrode to be attached; and S6, connecting the top cover with the current collecting net and covering the opening of the shell. In the technical scheme, the use of solvents is reduced, the processing technology is simple and convenient, and the method is suitable for large-scale production and has good economic effect.
Description
Technical Field
The present application relates to the field of solid-state batteries, and more particularly, to a sulfide-based solid electrolyte all-solid-state battery and a method for manufacturing the same.
Background
The all-solid-state lithium battery has the excellent performances of high energy density, good safety, wide working temperature range, long cycle life and the like, and has become a research and development hotspot of domestic and foreign enterprises and scientific research institutions.
At present, the all-solid-state lithium battery mainly has two preparation methods, one is to form the battery through sulfide layer-by-layer pressure, the method has the advantages of low production efficiency, high production cost, difficult realization of battery measurement, high electrolyte thickness and high battery internal resistance, and is not beneficial to large-scale production.
The other method is to prepare the material by a solvent method, the solvent method is convenient to produce, and the material is mixed and dispersed by a solvent to obtain slurry, and the slurry is coated and dried to obtain each part of the battery. Due to the high reactivity of the sulfide electrolyte, the traditional solvent such as NMP is not suitable, the selection of the solvent is limited to individual organic nonpolar solvents such as heptane, tetrahydrofuran and the like, the electric conductivity of the sulfide electrolyte is reduced due to the participation of a large amount of solvents, the sulfide electrolyte is easy to corrode containers and gloves, the safety is poor, and the cost is high.
Disclosure of Invention
In order to reduce the use of solvents in the processing process of the solid-state battery, the application provides a sulfide-based solid electrolyte all-solid-state battery and a preparation method thereof.
On one hand, the application provides a preparation method of a sulfide-based solid electrolyte all-solid-state battery, which specifically adopts the following technical scheme:
the preparation method of the sulfide-based solid electrolyte all-solid-state battery specifically comprises the following steps:
s1, preparing a positive electrode ring and a negative electrode rod;
s2, pressing the positive electrode ring into the cylindrical shell to be used as the positive electrode of the battery;
s3, coating the solid electrolyte membrane on the inner surface of the positive electrode ring and forming a membrane;
s4, pressing a negative rod with a current collecting net into the inner wall of the solid electrolyte membrane to be used as a negative electrode of the battery;
s5, further applying additional pressure to the negative pole rod to enable the positive pole ring, the negative pole rod and the solid electrolyte membrane to be attached;
s6, connecting the top cover with the flow collecting net and covering the opening of the shell;
the anode ring is prepared from the following raw materials in parts by weight:
1-3 parts of a solid electrolyte;
7-9 parts of a positive electrode material;
the cathode bar is prepared from the following raw materials in parts by weight:
1-3 parts of a solid electrolyte;
7-9 parts of a negative electrode material;
the anode ring comprises at least one anode ring unit, and the cathode bar comprises at least one cathode bar unit;
the solid electrolyte is one of LGPS or LPSCL, the positive electrode material is one of NCA or LCO, and the negative electrode material is one of graphite or silicon.
In the technical scheme, the anode ring and the cathode bar are respectively prepared, and the reddest finished battery is obtained through the process of sequentially pressing the solid anode ring and the solid cathode bar.
In the working process of the battery, the shell provides support and limit for the whole battery, extra pressure does not need to be provided for the battery in the using process, and the charging and discharging stability of the battery is further improved. In the process of charging and discharging the battery, the anode ring, the cathode bar and the electrolyte layer can be tightly attached, so that the resistance in the use process is reduced, and the service life of the battery is prolonged.
At the in-process that positive polar ring and negative pole stick pressed in battery case, if there are a plurality of positive polar ring units and negative pole stick unit, can together press in after piling up positive polar ring unit or negative pole stick unit, under the pressure effect, positive polar ring unit can integrate and form positive polar ring, and negative pole stick unit can integrate and form the negative pole stick, when being convenient for process, does not basically have the influence to holistic performance.
In step S5, by applying a certain additional pressure to the negative electrode, the bonding tightness between the negative electrode and the solid electrolyte, between the solid electrolyte and the positive electrode, and between the positive electrode and the case can be further increased, the interfacial resistance can be reduced, and the compactness and the conductivity of the solid electrolyte layer obtained by spraying can be further increased, thereby preventing the battery from short circuit.
Meanwhile, the battery prepared by the technical scheme is cylindrical, belongs to a more standardized battery, has a simpler production process and a wider application prospect compared with a battery (usually rectangular) prepared by a conventional lamination method, is easier to form a good butt joint with the existing surface conversion interface, and has a better application prospect.
Optionally, in step S1, the positive electrode ring unit is prepared by the following method:
weighing the positive electrode material and the solid electrolyte according to the formula, mixing for 20-40 min at normal temperature in a mixer, then pre-pressing, granulating and screening to obtain a positive electrode master batch, and then pressing and forming the positive electrode master batch through a tablet press to obtain the positive electrode ring unit.
In the technical scheme, the raw materials are pre-pressed and granulated firstly and then pressed, the whole raw materials are uniform and compact after pre-pressing and granulation, the pressure and the time required by the forming of the positive electrode ring are reduced, the strength of the prepared positive electrode ring is high, the positive electrode ring is not easy to crack and loose, and the quality of the all-solid-state battery is improved. And the above processes do not involve solvent, thus improving the safety of production and reducing the production cost.
Alternatively, in step S1, the negative electrode rod unit is prepared by the following method:
weighing the negative electrode material and the solid electrolyte according to the formula, mixing for 50-70 min at normal temperature in a mixer, then pre-pressing, granulating and screening to obtain negative electrode master batches, and performing high-pressure forming on the negative electrode master batches and the current collecting net through a tablet press to obtain the negative electrode rod unit.
In the above technical scheme, for the preparation of the negative electrode rod, a mode of prepressing, granulating, screening and then pressing after mixing is also adopted, and as the negative electrode material used in the negative electrode rod, graphite or silicon has poor dispersibility, a longer time is needed for mixing, a uniform negative electrode master batch can be obtained, and then pressing is carried out, so that the formed negative electrode rod has better strength and is not easy to crack or break.
Optionally, the ratio of the height to the outer diameter of each positive electrode ring unit is 0.5-1, and the ratio of the height to the outer diameter of each negative electrode rod unit is 0.75-1.5.
The positive pole ring unit and the negative pole rod unit are pressed in the size range, the forming difficulty is small, the production is convenient, and after the positive pole ring unit and the negative pole rod unit are stacked in the battery, the whole structure is compact, and the electrical performance of the manufactured battery is good.
Optionally, the pressure of the pre-pressing is 300-500 MPa in the preparation process of the positive master batch and the negative master batch, and the additional pressure applied to the negative rod is 600-700 MPa in step S5.
Among the above-mentioned technical scheme, in anodal master batch and negative pole master batch pressing process, the pre-compaction process can be accomplished betterly to 300~500 MPa's pressure, and on the one hand after the pre-compaction, solid-state electrolyte can be more even with anodal material or negative pole material mixture, and the clearance is better, and anodal master batch and the negative pole master batch form that the while preparation obtained are better, have positive influence to follow-up positive ring of suppression and negative pole stick. In addition, the additional pressure applied in step S5 is slightly greater than the pre-pressing pressure of the cathode master batches and the anode master batches in the preparation process, so that the cathode bar and the solid electrolyte membrane, the solid electrolyte membrane and the anode ring, and the cathode bar unit and the anode ring unit can be more tightly combined, and the reduction of the internal resistance of the battery is facilitated.
Optionally, in step S1, the particle sizes of the positive master batch and the negative master batch obtained by screening are 20 to 80 meshes.
The uniformity is better when 20 ~ 80 mesh anodal master batches and negative pole master batches are remixed, and has better grain type, and the area of contact between the anodal master batches and between the negative pole master batches is big in the follow-up pressing process, can improve anodal ring and negative pole stick intensity, and then reduces anodal rod and negative pole ring fracture, broken possibility.
Optionally, after the positive electrode ring and the negative electrode rod are subjected to compression molding, the density is not less than 90%.
The density is more than 90%, so that gaps in the positive electrode ring and the negative electrode rod can be effectively reduced, and the density of the positive electrode ring and the negative electrode ring and the battery performance of the prepared all-solid-state battery are improved.
Optionally, step S3 specifically includes the following steps:
s3-1, weighing the solid electrolyte, the polymer and the solvent according to the formula, and uniformly mixing to obtain stable slurry;
s3-2, spraying the stable slurry on the inner surface of the positive electrode ring;
s3-3, drying at 70-90 ℃ for 5-10 min, and quickly drying.
The solid electrolyte is dispersed through the polymer to form uniform and stable slurry, the slurry is coated on the inner surface of the positive electrode ring in a spraying mode, after the slurry is quickly dried, the coating can keep a uniform and stable state, the coating is not easy to crack under the action of tension, the formed solid electrolyte membrane is good in uniformity, and the battery performance is also good.
On the other hand, the application provides a sulfide-based solid electrolyte all-solid-state battery, which adopts the following technical scheme: the sulfide-based solid electrolyte all-solid-state battery is prepared by the preparation method of the sulfide-based solid electrolyte all-solid-state battery and comprises a cylindrical shell, wherein one end of the shell is opened and is covered by a top cover; the improved lithium battery is characterized in that a cathode bar is arranged in the shell, an anode ring is arranged around the outer ring of the cathode bar, a current collecting net is arranged between the cathode bar and the top cover, and a solid electrolyte membrane is arranged between the anode ring and the cathode bar.
In the technical scheme, the cylindrical shell is adopted, the processing is simple, the mechanical property is good, the yield of the obtained batteries in the processing process is high, and the method is suitable for large-scale production. Meanwhile, the cylindrical shell is mature in processing and bundling, low in cost and high in bending strength. Under conventional conditions, the battery with the cylindrical structure needs to be subjected to a complex process, and in the application, an all-solid-state mode is adopted, so that the process is simple, the production efficiency is improved, and the cost is greatly reduced.
Conductive carbon black is coated in the shell.
The conductive carbon black is beneficial to improving the corrosion resistance inside the steel shell, and is beneficial to improving the lubricity when the positive electrode ring is pressed into the steel shell, so that the yield is improved. Meanwhile, the conductive carbon black can enhance the current collecting effect of the steel shell on the positive pole ring and reduce the internal resistance of the battery.
In summary, the present application includes at least one of the following advantages:
1. in this application, adopt and suppress positive polar ring, negative pole stick respectively to the mode of coating electrolyte membrane on the positive polar ring produces full solid-state battery, helps simplifying the production technology of battery, reduces the use of solvent in the production process, thereby reduce cost, the casing also provides limiting displacement to the volume change of full solid-state battery in the charge-discharge cycle process simultaneously, promotes interface contact and circulation stability, and need not additionally exert pressure in battery work. .
2. In the application, the positive electrode ring unit and the negative electrode rod unit are prepared by mixing, prepressing, granulating and powder screening to prepare the positive electrode master batch or the negative electrode master batch, and then are obtained by pressing through a tablet press, so that the prepared positive electrode ring and negative electrode rod have high yield, are not easy to crack and break, and have good integral structure strength.
3. In this application, designed an all solid-state battery structure, adopted cylindrical casing, wholly be convenient for processing and standardized production, mechanical properties is also better.
Drawings
Fig. 1 is a schematic structural diagram of an all-solid-state battery in embodiments 1 to 36 of the present application.
In the figure, 1, a housing; 2. conductive carbon black; 3. a positive electrode ring; 4. a negative electrode bar; 5. a solid electrolyte membrane; 6. a current collecting network; 7. a top cover; 8. an insulating ring.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples.
Example 1, a sulfide-based solid electrolyte all-solid battery, referring to fig. 1, includes a case 1, a positive electrode ring 3 disposed in the case 1, a solid electrolyte membrane disposed in the positive electrode ring 3, and a negative electrode rod 4 disposed 5 inside the solid electrolyte membrane 5. Wherein, positive ring 3 is formed by stacking and pressing positive ring units, and negative rod 4 is formed by stacking and pressing negative rod units.
Referring to fig. 1, the housing 1 is a 18650 cylindrical nickel-plated steel case, and is open at the upper end and covered with a top cover 7. The inner wall of the housing 1 is coated with conductive carbon black 2. And the upper end of the negative rod 4 is provided with a current collecting net 6, and the current collecting net 6 is connected with the top cover 7 through welding. The current collecting net 6 is a stainless steel net, the top cover is a nickel-plated top cover, and the current collecting net is obtained by scribing, crimping and sealing. On the top cover, the facility has an insulating ring, in this embodiment a teflon ring, for isolating the top cover from the positive electrode ring, the solid electrolyte membrane and the housing.
The processing steps of the all-solid-state battery are as follows:
s1, preparing a positive electrode ring unit and a negative electrode rod unit;
s2, pressing the positive electrode ring unit into the shell coated with the conductive carbon black to form a positive electrode ring which is used as the positive electrode of the all-solid-state battery;
s3, coating the solid electrolyte membrane on the inner surface of the positive electrode ring and forming a membrane;
s4, pressing the negative pole rod with the current collecting net into the inner wall of the solid electrolyte membrane to be used as the negative pole of the battery;
s5, applying 600MPa extra pressure to the negative electrode to perform secondary pressing treatment;
and S6, welding the top cover and the current collecting net and covering the top cover and the current collecting net on the shell.
In step S1, the positive electrode ring unit is prepared as follows:
according to the following steps of 1: 7, weighing the solid electrolyte and the anode material, mixing for 30min in a mixer, pre-pressing under the pressure of 400MPa, granulating by a cutter, sieving and reserving the components of 20-80 meshes to obtain anode master batches, and pressing the anode master batches into a cylinder shape in a ring pressing machine by adopting the pressure of 1200MPa to obtain an anode ring unit.
The preparation method of the cathode bar unit comprises the following steps:
according to the following steps of 1: 7, weighing the solid electrolyte and the negative electrode material according to the mass ratio, mixing for 60min in a mixer, then pre-pressing under the pressure of 400MPa, then granulating by a cutter, sieving by a 50-mesh sieve to obtain negative electrode master batches, and pressing the negative electrode master batches into cylinders by adopting the pressure of 1000mPa in a tabletting machine to obtain a negative electrode rod unit; and one negative pole rod unit is pressed with the current collecting net by a tablet press in the pressing process.
Step S3 is specifically as follows:
s3-1, weighing the solid electrolyte and the polymer by taking xylene as a solvent, and slowly adding the solvent into a mixed system of the polymer and the solid electrolyte in a stirring state according to the mass ratio of the polymer to the solid electrolyte of 100:3 until stable slurry is obtained.
S3-2, uniformly spraying the stable slurry on the inner surface of the positive electrode ring, wherein the spraying thickness is 35 +/-5 microns.
S3-3, drying at 80 ℃ for 10min to finish the preparation of the solid electrolyte membrane.
In this embodiment, the positive electrode material is NCA, the negative electrode material is graphite, the solid electrolyte is LGPS, and the polymer is nitrile rubber. After the positive electrode ring and the negative electrode bar are pressed, the density of the positive electrode ring and the density of the negative electrode bar are both 95 +/-1 percent. After the preparation is finished, the height of a single positive electrode ring is 15mm, the total height of the positive electrode ring is 60mm, the inner diameter is 9mm, the outer diameter is 17.8mm, the height of a single negative electrode rod is 12.4mm, the total height of the negative electrode rod is 62mm, and the diameter is 8.9 mm. In the negative pole, only one side of the negative pole unit connected with the top cover facing the top cover is pressed with a current collecting net.
Examples 2 to 24, sulfide-based solid electrolyte all-solid-state batteries, which are different from example 1, are that the amounts of substances in the positive electrode ring and the negative electrode rod and the production parameters are shown in table 1.
TABLE 1 production parameters of all-solid-state batteries of examples 1 to 24 for positive electrode rings and negative electrode bars
For examples 1-24, the positive electrode ring and the negative electrode bar were subjected to strength and acceptable product characterization as shown in table 2.
TABLE 2, examples 1-24 electrode mechanical properties and qualification rate conditions
According to the experimental data, the anode ring and the cathode bar which are produced in a pressing mode have good strength, the water content is lower than 100ppm, the radial pressure is large, and cracking is not easy to occur. The mixing time of the raw materials and the pressure of the prepressing have a direct influence on the reject ratio and the radial pressure of the product. The fineness of the product has obvious influence on the dispersion time of the anode rod and the cathode ring in water, wherein the overall strength is lower due to overlarge particles, the contact area between the particles is small, the adhesion between the particles is not tight, the particles are easily dispersed in the water, the strength is lower, and the yield is also lower. If the particles are small, although the performance of the finally prepared positive electrode ring and negative electrode rod is not greatly influenced, the processing is troublesome, the equipment loss is large, and the method is not suitable for large-scale production, so that the particle sizes of the positive electrode master batch and the negative electrode master batch are preferably within the range of 20-80 meshes.
Based on example 1, further parameters were adjusted to obtain the following examples.
Examples 25 to 28, sulfide-based solid electrolyte all-solid-state batteries, which are different from example 1, are characterized in that parameters of the solid electrolyte membrane are shown in table 3.
Table 3, drying parameter tables in examples 25 to 28
| Numbering | Drying time (min) | Drying temperature (. degree.C.) |
| Example 1 | 10 | 80 |
| Example 25 | 5 | 70 |
| Example 26 | 10 | 90 |
| Example 27 | 20 | 60 |
| Example 28 | 5 | 100 |
Example 29, a sulfide-based solid electrolyte all-solid-state battery, differs from example 1 in that the compaction of the positive electrode rod and the negative electrode rod obtained by pressing were both 90 ± 1%.
Example 30, a sulfide-based solid electrolyte all-solid-state battery, differs from example 1 in that the compaction of the positive electrode rod and the negative electrode rod obtained by pressing were both 85 ± 1%.
Examples 31 to 36, sulfide-based solid electrolyte all-solid-state batteries, which are different from example 1 in the specific specifications of the batteries, are shown in table 4.
TABLE 4 list of the battery specifications of examples 31 to 36
Example 37, a sulfide-based solid electrolyte all-solid-state battery, differs from example 1 in that in step S5, the additional pressure is 700 mPa.
For the above examples, comparative examples were set as follows:
comparative example 1, sulfide-based solid electrolyte all-solid battery, which is different from example 1 in the structure of the battery. The all-solid-state battery adopts a lamination mode, a positive plate and a negative plate are obtained by pressing according to the proportion of a positive electrode and a negative electrode in example 1, a solid electrolyte membrane is coated on the positive plate, the negative plate is pressed on one surface of the positive plate coated with the solid electrolyte membrane after drying, and the negative plate and the positive plate are pressed together and then dried in an oven. The theoretical capacitance of the prepared all-solid-state electrolyte is 1835 mAh.
Comparative example 2, sulfide-based solid electrolyte all-solid battery, which is different from example 1, is that the positive electrode of the all-solid battery is manufactured in the following method by mixing the positive electrode material and the solid electrolyte, slowly adding n-heptane as a solvent and uniformly stirring until a uniform and stable slurry is formed, then coating the slurry on the inner surface of the case, and then vacuum-drying at 80 ℃ for 12 hours. The preparation method of the negative electrode is not changed.
Comparative example 3, a sulfide solid electrolyte all-solid battery, differs from example 1 in that step S5 is eliminated, and step S6 is directly performed after the negative electrode rod is pressed into the inner wall of the solid electrolyte membrane in step S4.
For the above examples, representative parts were selected and the performance test of the battery was performed as follows: 1. the cycle retention of the above lithium battery was measured after 300 cycles of charging at 25 ℃ by 0.1C/discharging by 0.1C.
2. The internal resistance of the lithium battery was measured after 300 cycles of charging at 25 ℃ by 0.1C/discharging by 0.1C.
In the application, the dosage of the solvent is reduced, so that compared with the comparative example 2, the residual solvent in the system is reduced, the cycle retention rate of the battery is improved to more than 90%, the internal resistance is also obviously reduced, and the performance of the battery is obviously improved. In example 30, the density of the positive electrode ring and the negative electrode rod is low, the cycle retention rate is greatly reduced, the internal resistance is increased, and it is proved that the good effect is achieved when the density of the positive electrode ring and the negative electrode rod is more than 90%. In addition, in comparative example 3, the contact between the negative electrode rod and the solid electrolyte membrane was not sufficiently tight due to the absence of step S5, thus causing a significant increase in the internal resistance of the cell.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The preparation method of the sulfide-based solid electrolyte all-solid-state battery is characterized by comprising the following steps of:
s1, preparing a positive electrode ring and a negative electrode rod;
s2, pressing the positive electrode ring into the cylindrical shell to be used as the positive electrode of the battery;
s3, coating the solid electrolyte membrane on the inner surface of the positive electrode ring and forming a membrane;
s4, pressing a negative rod with a current collecting net into the inner wall of the solid electrolyte membrane to be used as a negative electrode of the battery;
s5, further applying additional pressure to the negative pole rod to enable the positive pole ring, the negative pole rod and the solid electrolyte membrane to be attached;
s6, connecting the top cover with the flow collecting net and covering the opening of the shell;
the anode ring is prepared from the following raw materials in parts by weight:
1-3 parts of a solid electrolyte;
7-9 parts of a positive electrode material;
the cathode bar is prepared from the following raw materials in parts by weight:
1-3 parts of a solid electrolyte;
7-9 parts of a negative electrode material;
the anode ring comprises a plurality of anode ring units, and the cathode bar comprises a plurality of cathode bar units;
the solid electrolyte is one of LGPS or LPSCl, the positive electrode material is one of NCA or LCO, and the negative electrode material is one of graphite or silicon.
2. The method for producing a sulfide-based solid electrolyte all-solid battery according to claim 1, wherein in step S1, the positive electrode ring unit is produced by:
weighing the positive electrode material and the solid electrolyte according to the formula, mixing for 20-40 min at normal temperature in a mixer, then pre-pressing, granulating and screening to obtain a positive electrode master batch, and then pressing and forming the positive electrode master batch through a tablet press to obtain the positive electrode ring unit.
3. The production method of the sulfide-based solid electrolyte all-solid battery according to claim 2, wherein in step S1, the negative electrode rod unit is produced by:
weighing the negative electrode material and the solid electrolyte according to the formula, mixing for 50-70 min at normal temperature in a mixer, then pre-pressing, granulating and screening to obtain negative electrode master batches, and performing high-pressure forming on the negative electrode master batches and the current collecting net through a tablet press to obtain the negative electrode rod unit.
4. The method for producing a sulfide-based solid electrolyte all-solid battery according to claim 3, wherein a height to outside diameter ratio of each positive electrode ring unit is 0.5 to 1, and a height to outside diameter ratio of each negative electrode rod unit is 0.75 to 1.5.
5. The method for preparing the sulfide-based solid electrolyte all-solid battery according to claim 3, wherein the pressure of the pre-pressing of the positive electrode ring unit and the negative electrode rod unit is 300-500 MPa in the preparation process; in step S5, the pressure applied to the negative electrode bar is 600 to 700 MPa.
6. The method for preparing the sulfide-based solid electrolyte all-solid battery according to claim 3, wherein in step S1, the particle sizes of the positive electrode master batch and the negative electrode master batch obtained by screening are 20-80 meshes.
7. The production method of the sulfide-based solid electrolyte all-solid battery according to claim 3, wherein the positive electrode ring unit and the negative electrode rod unit have a compactness of not less than 90% after press-forming.
8. The method for producing a sulfide-based solid electrolyte all-solid battery according to claim 1, wherein step S3 specifically includes the steps of:
s3-1, weighing the solid electrolyte, the polymer and the solvent according to the formula, and uniformly mixing to obtain stable slurry;
s3-2, spraying the stable slurry between the positive electrode ring and the negative electrode rod;
s3-3, drying at 70-90 ℃ for 5-10 min, and quickly drying.
9. The sulfide-based solid electrolyte all-solid-state battery according to any one of claims 1 to 8, which is produced by the production method for a sulfide-based solid electrolyte all-solid-state battery, and which comprises a cylindrical case that is open at one end and covered with a top cover; the improved lithium battery is characterized in that a cathode bar is arranged in the shell, an anode ring is arranged around the outer ring of the cathode bar, a current collecting net is arranged between the cathode bar and the top cover, a solid electrolyte membrane is arranged between the anode ring and the cathode bar, and insulating rings are arranged between the top cover and the anode ring, and between the solid electrolyte membrane and the shell.
10. The sulfide-based solid electrolyte all-solid battery according to claim 9, wherein conductive carbon black is coated in the case.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1267925A (en) * | 1999-03-12 | 2000-09-27 | 索尼株式会社 | Solid electrolytic battery |
| CN1950968A (en) * | 2004-05-14 | 2007-04-18 | 松下电器产业株式会社 | Lithium ion secondary battery |
| CN102306842A (en) * | 2011-09-08 | 2012-01-04 | 浙江吉能电池科技有限公司 | Manufacturing method of cylindrical lithium ion battery |
| CN105609782A (en) * | 2015-12-17 | 2016-05-25 | 中国电子科技集团公司第十八研究所 | All-solid-state battery, and current collector and preparation method therefor |
| CN106252583A (en) * | 2016-08-31 | 2016-12-21 | 中银（宁波）电池有限公司 | A kind of pressure setting of anode ring |
| CN109320216A (en) * | 2018-11-06 | 2019-02-12 | 江苏中正陶瓷科技有限公司 | A kind of calcium hexaluminate crucible manufacturing modified based on laminar structured rare earth oxide |
| CN111313101A (en) * | 2019-10-25 | 2020-06-19 | 浙江锋锂新能源科技有限公司 | Low-internal-resistance solid sulfide electrolyte lithium battery cell, battery and preparation method thereof |
-
2021
- 2021-04-25 CN CN202110450552.2A patent/CN113394463A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1267925A (en) * | 1999-03-12 | 2000-09-27 | 索尼株式会社 | Solid electrolytic battery |
| CN1950968A (en) * | 2004-05-14 | 2007-04-18 | 松下电器产业株式会社 | Lithium ion secondary battery |
| CN102306842A (en) * | 2011-09-08 | 2012-01-04 | 浙江吉能电池科技有限公司 | Manufacturing method of cylindrical lithium ion battery |
| CN105609782A (en) * | 2015-12-17 | 2016-05-25 | 中国电子科技集团公司第十八研究所 | All-solid-state battery, and current collector and preparation method therefor |
| CN106252583A (en) * | 2016-08-31 | 2016-12-21 | 中银（宁波）电池有限公司 | A kind of pressure setting of anode ring |
| CN109320216A (en) * | 2018-11-06 | 2019-02-12 | 江苏中正陶瓷科技有限公司 | A kind of calcium hexaluminate crucible manufacturing modified based on laminar structured rare earth oxide |
| CN111313101A (en) * | 2019-10-25 | 2020-06-19 | 浙江锋锂新能源科技有限公司 | Low-internal-resistance solid sulfide electrolyte lithium battery cell, battery and preparation method thereof |
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Application publication date: 20210914 |