An additive manufacturing method for all-solid-state batteries

Abstract

The present invention relates to the technical field of solid-state batteries, and in particular to an additive manufacturing method for all-solid-state batteries, comprising: forming positive electrode slurry, negative electrode slurry, electrolyte slurry and current collector slurry; forming each primary solid-state battery assembly; post-processing each primary solid-state battery assembly to form a finished solid-state battery; obtaining several quality test results of the finished solid-state battery; determining the additive manufacturing state according to the proportion of the number of unqualified products in the quality test; if the additive manufacturing state is unstable, adjusting the cutting distance or determining whether the slurry solidification state meets the requirements in combination with the surface inclination of the primary solid-state battery assembly; if the slurry solidification state does not meet the requirements, adjusting the printing speed of the additive device according to the surface inclination of the primary solid-state battery assembly or adjusting the rising rate of the stirring blade according to the maximum average flow distance of the slurry. The present invention achieves the improvement of additive manufacturing accuracy and slurry stability.

Description

Technical Field

[0001] The present invention relates to the technical field of solid-state batteries, and in particular to an additive manufacturing method for all-solid-state batteries. Background Art

[0002] In the existing technology, although all-solid-state batteries have many advantages in theory, they still face challenges in energy density, power density, cycle life, etc. in practical applications. At present, the manufacture of all-solid-state batteries mainly relies on traditional physical or chemical methods, which have limitations in preparing batteries with complex shapes and structures. Although the emerging 3D printing technology has the ability to manufacture complex structures, its accuracy needs to be further improved.

[0003] Chinese patent publication number: CN115458806A discloses a composite electrolyte solid-state battery and its additive manufacturing method, comprising: a positive electrode current collector, a positive electrode, a negative electrode, a negative electrode current collector and a composite electrolyte; the composite electrolyte is mainly made of a composite electrolyte slurry composed of polyethylene oxide, lithium salt, an inorganic solid electrolyte, an aqueous photosensitive resin and a photoinitiator; in the composite electrolyte slurry, the photoinitiator is 0.8 of the mass of the aqueous photosensitive resin 1.5%, the molar ratio of polyethylene oxide to lithium salt is 15:1 20:1, the porous inorganic solid electrolyte particles are 10% of the mass of polyethylene oxide 30%, polyethylene oxide accounts for 55% of the total volume of the slurry 75%. It can be seen that the composite electrolyte solid-state battery and its additive manufacturing method have the problems of low additive manufacturing state accuracy and unstable slurry curing state. Summary of the invention

[0004] To this end, the present invention provides an additive manufacturing method for all-solid-state batteries, so as to overcome the problems of unstable additive manufacturing state and unstable slurry curing state in the prior art.

[0005] To achieve the above-mentioned purpose, the present invention provides an additive manufacturing method for an all-solid-state battery, comprising: respectively mixing and stirring a positive electrode raw material, a negative electrode raw material, an electrolyte raw material and a current collector raw material in sequence to form a positive electrode slurry, a negative electrode slurry, an electrolyte slurry and a current collector slurry; using an additive device pre-set with solid-state battery structural parameters to print the positive electrode slurry, the negative electrode slurry, the electrolyte slurry and the current collector slurry to form a primary solid-state battery component corresponding to each of the slurries; post-processing each of the primary solid-state battery components to form a finished solid-state battery; obtaining several quality test results of the finished solid-state battery within a unit cycle; determining the additive manufacturing quality according to the proportion of the number of unqualified products in the quality test. state; if the additive manufacturing state is determined to be unstable, the cutting distance is adjusted or the surface inclination of the primary solid-state battery component currently output by the additive is combined to determine whether the slurry solidification state meets the requirements; if the slurry solidification state does not meet the requirements, the printing speed of the additive device is adjusted according to the surface inclination of the primary solid-state battery component or the rising rate of the stirring blade is adjusted according to the maximum average flow distance of the slurry; wherein, the cutting distance is the vertical distance between the cutting position when the primary solid-state battery component is cut and the bottom end of the primary solid-state battery component; wherein, the maximum average flow distance of the slurry is the farthest distance that the slurry can flow on a smooth test plane without adding external force after stirring.

[0006] Furthermore, the post-processing process includes:

[0007] Cutting and grinding, separating and grinding the primary solid-state battery component from the support structure formed during the printing process by a mechanical tool;

[0008] Combining, combining the primary solid-state battery components to form the finished solid-state battery;

[0009] Curing annealing: the internal stress generated during the additive process is eliminated through the curing annealing process;

[0010] Surface modification, cleaning, passivating or coating the surface of the finished solid-state battery with a protective film;

[0011] Packaging: Packaging the finished solid-state battery to isolate it from the external environment.

[0012] Furthermore, the step of determining whether the additive manufacturing state meets the requirements includes:

[0013] Obtain the number of unqualified products and the total number of products from several quality test results within a unit cycle of the finished solid-state battery, and calculate the proportion of the number of unqualified products based on the obtained results;

[0014] Determine the additive manufacturing status according to the percentage of the number of unqualified products;

[0015] If the proportion of the number of unqualified products is greater than the preset first proportion, the additive manufacturing state is determined to be unstable; if the proportion of the number of unqualified products is less than or equal to the preset first proportion, the additive manufacturing state is determined to be stable.

[0016] Further, the step of determining whether the slurry solidification state meets the requirements in combination with the surface inclination of the primary solid-state battery assembly includes:

[0017] Compare the percentage of the number of unqualified products with the preset first percentage and the preset second percentage respectively;

[0018] If the proportion of the number of unqualified products is greater than or equal to the preset first proportion and less than or equal to the preset second proportion, it is determined that the slurry solidification state does not meet the requirements, and the slurry solidification state is secondary determined according to the surface inclination of the primary solid-state battery assembly;

[0019] Among them, the preset first quantity proportion is smaller than the preset second quantity proportion; the unqualified quantity proportion is the ratio of the number of unqualified products in the number of products in a unit period to the total number of products.

[0020] Furthermore, the step of adjusting the cutting distance includes:

[0021] Comparing the percentage of the number of unqualified products with the preset second percentage of the number;

[0022] If the proportion of the number of unqualified products is greater than the preset second proportion, the cutting distance is increased.

[0023] Furthermore, judging whether the solidification state of the slurry meets the requirements in combination with the surface inclination of the primary solid-state battery component includes:

[0024] Obtaining the surface inclination of the primary solid-state battery assembly;

[0025] Comparing the surface inclination of the primary solid-state battery assembly with a preset first surface inclination and a preset second surface inclination respectively;

[0026] If the surface inclination is greater than the preset first surface inclination and less than or equal to the preset second surface inclination, it is determined that the slurry solidification state does not meet the requirements, and the rising rate of the stirring blade is adjusted according to the maximum average flow distance of the slurry.

[0027] Furthermore, the step of adjusting the printing speed of the additive device includes:

[0028] comparing the surface inclination with a preset second surface inclination;

[0029] If the surface inclination is greater than a preset second surface inclination, reducing the printing speed of the additive device;

[0030] Wherein, the preset first surface inclination is smaller than the preset second surface inclination;

[0031] Wherein, the printing speed of the additive device is proportional to the inclination of the surface.

[0032] Further, the step of adjusting the rising speed of the stirring blade according to the maximum average flow distance of the slurry comprises:

[0033] Obtain the maximum average flow distance of each type of slurry and the number of slurry types;

[0034] Calculating the maximum average flow distance of the slurry according to the obtained results;

[0035] comparing the maximum average flow distance of the slurry with a preset maximum average flow distance;

[0036] If the maximum average flow distance is greater than the preset maximum average flow distance, it is determined that the slurry fluidity does not meet the requirements, and the rising rate of the stirring blade is increased.

[0037] Furthermore, the maximum average flow distance of the slurry is proportional to the rising rate of the stirring blade.

[0038] Furthermore, the mass proportion of the primary solidified material in the positive electrode slurry, the negative electrode slurry, the electrolyte slurry and the current collector slurry is much greater than the mass proportion of the secondary solidified material;

[0039] Wherein, the primary curing material is a photosensitive resin, and the secondary curing material includes a photochemical agent, a binder and an additive.

[0040] Compared with the prior art, the beneficial effect of the present invention lies in that the method of the present invention, by setting a processing step for determining whether the stability of the additive manufacturing state meets the requirements, the shear stress generated in the stage of post-processing and cutting off the support structure of the preliminary solid-state battery assembly will cause the preliminary solid-state battery assembly to deform before it is fully solidified, thereby affecting the mechanical properties of the preliminary solid-state battery assembly, and by increasing the cutting distance of the primary solid-state battery when the additive manufacturing state does not meet the requirements, the influence of the cutting shear stress on the preliminary solid-state battery assembly is reduced; in the processing step for determining whether the slurry solidification state meets the requirements, in the process of printing the preliminary solid-state battery assembly, the slurry is heated and melted by the nozzle in the additive equipment and then sprayed onto the lower layer to be formed on the preliminary solid-state battery assembly structure to be cooled and solidified to form the preliminary solid-state battery assembly, in this process, the melted slurry releases heat in the air during the process of being sprayed from the nozzle, and at this time, the printing speed determines the amount of slurry that is being heat-released and solidified, and more heat release leads to an increase in the ambient temperature in the additive equipment bin, and the high temperature environment is not conducive to the cooling and solidification of the slurry, thereby causing the surface inclination of the produced preliminary solid-state battery to increase, and the rising rate of the stirring blade is increased by reducing the printing speed or increasing the maximum average flow distance of the slurry.

[0041] Furthermore, the method of the present invention makes the printed battery structure more stable through a post-processing process, improves the close bonding between the electrolyte and the electrode materials, improves the performance and stability of the solid-state battery, enhances the corrosion resistance and conductivity of the battery, and further achieves the improvement of the battery's service life.

[0042] Furthermore, the method of the present invention further reduces the impact of external shear stress on battery performance and improves the proportion of qualified solid-state battery products in the production process by increasing the cutting distance when the proportion of unqualified products is greater than a preset second proportion.

[0043] Furthermore, the method of the present invention further reduces the interface resistance between the components of the solid-state battery by reducing the printing speed of the additive device when the surface inclination is greater than the preset second surface inclination, thereby improving the ion transmission efficiency, so that the battery can be charged and discharged more quickly. The small surface inclination makes the electrolyte layer uniform and dense, reducing the occurrence of electrolyte leakage and internal short circuit of the battery.

[0044] Furthermore, the method of the present invention increases the rising rate of the stirring blade according to the maximum average flow distance of the slurry when the surface inclination is greater than the preset first surface inclination and less than the preset second surface inclination, so that the resin component in the slurry can be volatilized during the stirring process, thereby enhancing the curing speed and curing state of the slurry in the additive equipment, and achieving improved production quality and production efficiency.

[0045] Furthermore, the method of the present invention sets photosensitive resin as the main curing material, so that the slurry can adapt to the additive equipment, and has small curing shrinkage, high moisture strength and small swelling, thereby reducing problems such as part deformation, warping, cracking, and the occurrence of deformation, expansion and interlayer delamination during the curing process, and reducing the dimensional deviation of wet molded parts in liquid resin, thereby further improving the accuracy of molded parts, enhancing the stability of parts, and improving the molding accuracy of all-solid-state batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 is a process flow chart of an additive manufacturing method for an all-solid-state battery according to an embodiment of the present invention;

[0047] Figure 2 This is a post-processing flow chart of an additive manufacturing method for an all-solid-state battery according to an embodiment of the present invention;

[0048] Figure 3 The present invention is a logical flow chart of an additive manufacturing method for all-solid-state batteries according to an embodiment of the present invention. DETAILED DESCRIPTION

[0049] In order to make the objects and advantages of the present invention more clearly understood, the present invention is further described below in conjunction with embodiments; it should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0050] The preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood by those skilled in the art that these embodiments are only used to explain the technical principles of the present invention and are not intended to limit the protection scope of the present invention.

[0051] It should be noted that, in the description of the present invention, terms such as "up", "down", "left", "right", "inside" and "outside" indicating directions or positional relationships are based on the directions or positional relationships shown in the drawings. This is merely for the convenience of description and does not indicate or imply that the device or element must have a specific orientation, be constructed and operated in a specific orientation. Therefore, it cannot be understood as a limitation on the present invention.

[0052] In addition, it should be noted that in the description of the present invention, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two components. For those skilled in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0053] See also Figure 1 , Figure 2 as well as Figure 3 As shown, they are respectively a process flow chart, a post-processing flow chart, and a logic flow chart of an additive manufacturing method for an all-solid-state battery according to an embodiment of the present invention. An additive manufacturing method for an all-solid-state battery according to the present invention comprises:

[0054] Step S1, respectively mixing and stirring the positive electrode raw material, the negative electrode raw material, the electrolyte raw material and the current collector raw material in sequence to form a positive electrode slurry, a negative electrode slurry, an electrolyte slurry and a current collector slurry;

[0055] Step S2, using an additive device with solid-state battery structure parameters preset, to print the positive electrode slurry, the negative electrode slurry, the electrolyte slurry and the current collector slurry to form a primary solid-state battery assembly corresponding to each slurry;

[0056] Step S3, post-processing each of the primary solid-state battery components to form a finished solid-state battery;

[0057] Step S4, obtaining several quality test results of the finished solid-state battery within a unit cycle;

[0058] Step S5, determining the additive manufacturing status according to the proportion of unqualified products in the quality test;

[0059] Step S6, if it is determined that the additive manufacturing state is unstable, the cutting distance is adjusted or the surface inclination of the primary solid-state battery component output by the current additive manufacturing is combined to determine whether the slurry solidification state meets the requirements;

[0060] Step S7, if the solidification state of the slurry does not meet the requirements, adjusting the printing speed of the additive device according to the surface inclination of the primary solid-state battery assembly or adjusting the rising rate of the stirring blade according to the maximum average flow distance of the slurry;

[0061] Wherein, the cutting distance is the vertical distance between the cutting position when the primary solid-state battery assembly is cut and the bottom end of the primary solid-state battery assembly is the cutting distance;

[0062] The maximum average flow distance of the slurry is the longest distance that a plurality of slurries can flow on a smooth test plane without adding external force after stirring.

[0063] Specifically, the structural parameters of solid-state batteries include the diameter, thickness and size of the battery cells.

[0064] Specifically, the additive device is a 3D printer.

[0065] In implementation, the method of the present invention sets a processing step for determining whether the stability of the additive manufacturing state meets the requirements. When the preliminary solid-state battery assembly is in the stage of post-processing and cutting off the support structure, the shear stress generated will cause the preliminary solid-state battery assembly to deform before it is fully solidified, thereby affecting the mechanical properties of the preliminary solid-state battery assembly. When the additive manufacturing state does not meet the requirements, the cutting distance of the primary solid-state battery is increased to reduce the influence of the cutting shear stress on the preliminary solid-state battery assembly. In the processing step for determining whether the slurry solidification state meets the requirements, in the process of printing the preliminary solid-state battery assembly, the slurry is heated and melted by the nozzle in the additive equipment and then sprayed onto the lower layer of the preliminary solid-state battery assembly structure to be formed to cool and solidify, thereby forming a preliminary solid-state battery assembly. In this process, the melted slurry releases heat in the air during the process of being sprayed from the nozzle. At this time, the printing speed determines the amount of slurry that is being heat-released and solidified. Excessive heat release leads to an increase in the ambient temperature in the additive equipment bin. The high temperature environment is not conducive to the cooling and solidification of the slurry, thereby increasing the surface inclination of the produced preliminary solid-state battery. The rising rate of the stirring blade is increased by reducing the printing speed or increasing the maximum average flow distance of the slurry.

[0066] Specifically, the post-processing process includes:

[0067] Cutting and grinding, separating and grinding the primary solid-state battery component from the support structure formed during the printing process by a mechanical tool;

[0068] Combining, combining the primary solid-state battery components to form the finished solid-state battery;

[0069] Curing annealing: the internal stress generated during the additive process is eliminated through the curing annealing process;

[0070] Surface modification, cleaning, passivating or coating the surface of the finished solid-state battery with a protective film;

[0071] Packaging: Packaging the finished solid-state battery to isolate it from the external environment.

[0072] In practice, the method of the present invention makes the printed battery structure more stable through a post-processing process, improves the close bonding between the electrolyte and the electrode materials, improves the performance and stability of the solid-state battery, enhances the corrosion resistance and conductivity of the battery, and further achieves the improvement of the battery's service life.

[0073] Specifically, in order to ensure the stability and integrity of the printing process, a support structure connected to the primary solid-state battery component will be formed during the additive process. Once printing is completed, the support structure needs to be removed in order to obtain the final printed product. In order to avoid damage to the primary solid-state battery component during the removal process, the cutting position of the support structure is selected by the mechanical tool to adjust the cutting distance.

[0074] Specifically, the maximum average flow distance of the slurry is obtained by testing the farthest distance that a unit volume of slurry can flow on a smooth test plane without adding external force.

[0075] Specifically, the mixer stirs the slurry horizontally through the stirring blades, and the stirring rod drives the stirring blades to stir the slurry at different vertical positions in the vertical direction at the same time, thereby adjusting the rising rate of the stirring blades.

[0076] Specifically, the step of determining whether the additive manufacturing state meets the requirements includes:

[0077] Obtain the number of unqualified products and the total number of products from several quality test results within a unit cycle of the finished solid-state battery, and calculate the proportion of the number of unqualified products based on the obtained results;

[0078] Determine the additive manufacturing status according to the percentage of the number of unqualified products;

[0079] If the proportion of the number of unqualified products is greater than the preset first proportion, the additive manufacturing state is determined to be unstable; if the proportion of the number of unqualified products is less than or equal to the preset first proportion, the additive manufacturing state is determined to be stable.

[0080] Specifically, when the all-solid-state batteries produced fail to meet the predetermined standards or market requirements in terms of energy density, charge and discharge efficiency, and cycle life performance indicators, and when there are errors in the appearance, size, and weight of the batteries, they are judged as unqualified products.

[0081] Specifically, the steps of determining whether the slurry solidification state meets the requirements in combination with the surface inclination of the primary solid-state battery component include:

[0082] Compare the percentage of the number of unqualified products with the preset first percentage and the preset second percentage respectively;

[0083] If the proportion of the number of unqualified products is greater than or equal to the preset first proportion and less than or equal to the preset second proportion, it is determined that the slurry solidification state does not meet the requirements, and the slurry solidification state is secondary determined according to the surface inclination of the primary solid-state battery assembly;

[0084] The proportion of the preset first quantity is smaller than the proportion of the preset second quantity;

[0085] Among them, the proportion of unqualified products is the ratio of the number of unqualified products to the total number of products in a unit period. The expression is:

[0086]

[0087] in, is the number of unqualified products in the unit period. is the total number of products in a unit period.

[0088] In implementation, the preset first quantity ratio is generally [0.002, 0.005], and the preset second quantity ratio is generally [0.008, 0.01].

[0089] Optionally, a preferred embodiment of the preset first quantity ratio is 0.003, and a preferred embodiment of the preset second quantity ratio is 0.009.

[0090] In implementation, the method of the present invention further reduces the impact of external shear stress on battery performance and improves the proportion of qualified solid-state battery products in the production process by increasing the cutting distance when the proportion of unqualified products is greater than a preset second proportion.

[0091] Specifically, the step of adjusting the cutting distance includes:

[0092] Comparing the percentage of the number of unqualified products with the preset second percentage of the number;

[0093] If the proportion of the number of unqualified products is greater than the preset second proportion, the cutting distance is increased.

[0094] In a specific embodiment, the proportion of unqualified numbers is 0.003 greater than the preset second number, and the cutting distance is increased by 2 mm compared with the current cutting distance. When the proportion of unqualified numbers exceeds 0.003 of the second number, the cutting distance increases by 0.5 mm for every 0.001 exceeding it. For example, when the proportion of unqualified numbers is 0.0014, the cutting distance increases to 2+0.5×2=3 mm.

[0095] Specifically, the surface inclination of the primary solid-state battery component is combined to determine whether the slurry solidification state meets the requirements, including:

[0096] Obtaining the surface inclination of the primary solid-state battery assembly;

[0097] Comparing the surface inclination of the primary solid-state battery assembly with a preset first surface inclination and a preset second surface inclination respectively;

[0098] If the surface inclination is greater than the preset first surface inclination and less than or equal to the preset second surface inclination, it is determined that the slurry solidification state does not meet the requirements, and the rising rate of the stirring blade is adjusted according to the maximum average flow distance of the slurry.

[0099] Specifically, the steps of adjusting the printing speed of the additive device include:

[0100] comparing the surface inclination with a preset second surface inclination;

[0101] If the surface inclination is greater than a preset second surface inclination, reducing the printing speed of the additive device;

[0102] Wherein, the preset first surface inclination is smaller than the preset second surface inclination;

[0103] Wherein, the printing speed of the additive device is proportional to the inclination of the surface.

[0104] Specifically, the surface inclination of the primary solid-state battery component is determined by measuring with a surface inclination sensor, wherein the surface inclination sensor is connected to the primary solid-state battery component.

[0105] Specifically, the printing speed of additive equipment is generally [90mm / s, 150mm / s].

[0106] In implementation, the preset first surface inclination is generally (140 μm, 180 μm), and the preset second surface inclination is generally (200 μm, 240 μm).

[0107] Optionally, a preferred embodiment of the preset first surface inclination is 160 μm, and a preferred embodiment of the preset second surface inclination is 220 μm.

[0108] In implementation, for every 10 μm that the surface inclination exceeds the second surface inclination, the printing speed of the additive device is reduced by 5 mm / s. For example, when the surface inclination is 260 μm, the printing speed is reduced to 150-4×5=130 mm / s.

[0109] In implementation, the method of the present invention further reduces the interface resistance between the components of the solid-state battery by reducing the printing speed of the additive device when the surface inclination is greater than the preset second surface inclination, thereby improving the ion transmission efficiency, so that the battery can be charged and discharged more quickly. The small surface inclination makes the electrolyte layer uniform and dense, reducing the occurrence of electrolyte leakage and internal short circuit of the battery.

[0110] Specifically, the step of adjusting the rising speed of the stirring blade according to the maximum average flow distance of the slurry comprises:

[0111] Obtain the maximum average flow distance of each type of slurry and the number of slurry types;

[0112] Calculating the maximum average flow distance of the slurry according to the obtained results;

[0113] comparing the maximum average flow distance of the slurry with a preset maximum average flow distance;

[0114] If the maximum average flow distance is greater than the preset maximum average flow distance, it is determined that the slurry fluidity does not meet the requirements, and the rising rate of the stirring blade is increased.

[0115] Specifically, the maximum average flow distance of the slurry is proportional to the rising speed of the stirring blade.

[0116] Specifically, the formula for the maximum flow distance of the slurry is:

[0117]

[0118] Where d is the maximum flow distance of the slurry, is the maximum flow distance of the positive electrode slurry detected for the i-th time, is the maximum flow distance of the negative electrode slurry detected for the i-th time, is the maximum flow distance of the electrolyte slurry detected for the i-th time, is the maximum flow distance of the collector slurry detected for the i-th time, n is the number of measurements, and n is a natural number greater than 1.

[0119] Specifically, the preset maximum average flow distance is generally (0.1m, 0.14m).

[0120] Optionally, a preferred embodiment of the preset maximum average flow distance is 0.12 m.

[0121] During implementation, for every 0.01 m that the maximum average flow distance of the slurry exceeds the preset maximum average flow distance, the speed of the stirring blade increases by 0.02 m / s. For example, when the maximum average flow distance of the slurry is 0.016 m, the rising speed of the stirring blade increases to 2 m / s + 0.02 × 4 = 2.08 m / s.

[0122] In implementation, the method of the present invention increases the rising rate of the stirring blade according to the maximum average flow distance of the slurry when the surface inclination is greater than the preset first surface inclination and less than the preset second surface inclination, so that the resin component in the slurry can be volatilized during the stirring process, thereby enhancing the curing speed and curing state of the slurry in the additive equipment, and achieving improved production quality and production efficiency.

[0123] Specifically, the mass proportion of the primary solidified material in the positive electrode slurry, the negative electrode slurry, the electrolyte slurry and the current collector slurry is much greater than the mass proportion of the secondary solidified material;

[0124] Wherein, the primary curing material is a photosensitive resin, and the secondary curing material includes a photochemical agent, a binder and an additive.

[0125] In implementation, the method of the present invention sets photosensitive resin as the main curing material so that the slurry can adapt to the additive equipment, and has small curing shrinkage, high humidity strength and small swelling, thereby reducing problems such as part deformation, warping, and cracking, reducing the occurrence of deformation, expansion and interlayer delamination during the curing process, and reducing the dimensional deviation of wet molded parts in liquid resin, thereby further improving the accuracy of molded parts, enhancing the stability of parts, and improving the molding accuracy of all-solid-state batteries.

[0126] So far, the technical solutions of the present invention have been described in conjunction with the preferred embodiments shown in the accompanying drawings. However, it is easy for those skilled in the art to understand that the protection scope of the present invention is obviously not limited to these specific embodiments. Without departing from the principle of the present invention, those skilled in the art can make equivalent changes or substitutions to the relevant technical features, and the technical solutions after these changes or substitutions will fall within the protection scope of the present invention.

Claims

1. An additive manufacturing method for an all-solid-state battery, characterized in that: The following steps are involved: The positive electrode raw material, the negative electrode raw material, the electrolyte raw material and the current collector raw material are mixed and stirred in sequence to form a positive electrode slurry, a negative electrode slurry, an electrolyte slurry and a current collector slurry; Using an additive device with solid-state battery structure parameters preset, the positive electrode slurry, the negative electrode slurry, the electrolyte slurry and the current collector slurry are printed to form primary solid-state battery components corresponding to each slurry; Post-processing each of the primary solid-state battery components to form a finished solid-state battery; Obtaining several quality test results of the finished solid-state battery within a unit cycle; Determine the additive manufacturing status based on the percentage of unqualified products in the quality test; If the additive manufacturing state is determined to be unstable, the cutting distance is adjusted or the surface inclination of the primary solid-state battery component output by the current additive manufacturing is combined to determine whether the slurry solidification state meets the requirements; If the solidification state of the slurry does not meet the requirements, the printing speed of the additive device is adjusted according to the surface inclination of the primary solid-state battery component or the rising rate of the stirring blade is adjusted according to the maximum average flow distance of the slurry; Wherein, the cutting distance is the vertical distance between the cutting position when the primary solid-state battery assembly is cut and the bottom end of the primary solid-state battery assembly is the cutting distance; The maximum average flow distance of the slurry is the longest distance that the stirred slurry can flow on a smooth test plane without adding external force.

2. The additive manufacturing method for all-solid-state batteries according to claim 1, characterized in that: The post-processing process includes: Cutting and grinding, separating and grinding the primary solid-state battery component from the support structure formed during the printing process by a mechanical tool; Combining, combining the primary solid-state battery components to form the finished solid-state battery; Curing annealing: the internal stress generated during the additive process is eliminated through the curing annealing process; Surface modification: cleaning, passivating or coating the surface of the finished solid-state battery with a protective film; Packaging: Packaging the finished solid-state battery to isolate it from the external environment.

3. The additive manufacturing method for all-solid-state batteries according to claim 1, characterized in that: The step of determining whether the additive manufacturing state meets the requirements includes: Obtain the number of unqualified products and the total number of products from the quality test results of several times within a unit cycle of the finished solid-state battery, and calculate the proportion of the number of unqualified products based on the number of unqualified products and the total number of products; Determine the additive manufacturing status according to the percentage of the number of unqualified products; If the proportion of the number of unqualified products is greater than the preset first proportion, the additive manufacturing state is determined to be unstable; if the proportion of the number of unqualified products is less than or equal to the preset first proportion, the additive manufacturing state is determined to be stable.

4. The additive manufacturing method for all-solid-state batteries according to claim 3, characterized in that: The steps of determining whether the slurry solidification state meets the requirements in combination with the surface inclination of the primary solid-state battery component include: Compare the percentage of the number of unqualified products with the preset first percentage and the preset second percentage respectively; If the proportion of the number of unqualified products is greater than or equal to the preset first proportion and less than or equal to the preset second proportion, it is determined that the slurry solidification state does not meet the requirements, and the slurry solidification state is secondary determined according to the surface inclination of the primary solid-state battery assembly; Among them, the preset first quantity proportion is smaller than the preset second quantity proportion; the unqualified quantity proportion is the ratio of the number of unqualified products in the number of products in a unit period to the total number of products.

5. The additive manufacturing method for all-solid-state batteries according to claim 4, characterized in that: The step of adjusting the cutting distance comprises: Comparing the percentage of the number of unqualified products with the preset second percentage of the number; If the proportion of the number of unqualified products is greater than the preset second proportion, the cutting distance is increased.

6. The additive manufacturing method for all-solid-state batteries according to claim 5, characterized in that: Combined with the surface inclination of the primary solid-state battery component, determine whether the slurry solidification state meets the requirements, including: Obtaining the surface inclination of the primary solid-state battery assembly; Comparing the surface inclination of the primary solid-state battery assembly with a preset first surface inclination and a preset second surface inclination respectively; If the surface inclination is greater than the preset first surface inclination and less than or equal to the preset second surface inclination, it is determined that the slurry solidification state does not meet the requirements, and the rising rate of the stirring blade is adjusted according to the maximum average flow distance of the slurry.

7. The additive manufacturing method for all-solid-state batteries according to claim 6, characterized in that: The steps for adjusting the printing speed of the additive equipment include: comparing the surface inclination with a preset second surface inclination; If the surface inclination is greater than a preset second surface inclination, reducing the printing speed of the additive device; Wherein, the preset first surface inclination is smaller than the preset second surface inclination; Wherein, the printing speed of the additive device is proportional to the inclination of the surface.

8. The additive manufacturing method for all-solid-state batteries according to claim 6, characterized in that: The step of adjusting the rising speed of the stirring blade according to the maximum average flow distance of the slurry comprises: Obtain the maximum average flow distance of each type of slurry and the number of slurry types; Calculating the maximum average flow distance of the slurry according to the maximum average flow distance of each type of slurry and the number of types of slurry; comparing the maximum average flow distance of the slurry with a preset maximum average flow distance; If the maximum average flow distance is greater than the preset maximum average flow distance, it is determined that the slurry fluidity does not meet the requirements, and the rising rate of the stirring blade is increased.

9. The additive manufacturing method for all-solid-state batteries according to claim 8, characterized in that: The maximum average flow distance of the slurry is proportional to the rising speed of the stirring blade.

10. The additive manufacturing method for all-solid-state batteries according to claim 1, characterized in that: The mass proportion of the primary solidified material in the positive electrode slurry, the negative electrode slurry, the electrolyte slurry and the current collector slurry is much greater than the mass proportion of the secondary solidified material; Wherein, the primary curing material is a photosensitive resin, and the secondary curing material includes a photochemical agent, a binder and an additive.

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