CN112186262B - MLCC structure-based all-solid-state lithium ion battery and preparation method thereof - Google Patents
MLCC structure-based all-solid-state lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an all-solid-state lithium ion battery based on an MLCC structure and a preparation method thereof. And connecting the obtained all-solid-state battery monomers in series or in parallel in a lamination mode, and then performing hot-press molding to obtain the all-solid-state battery with the MLCC structure. By LiVPO 4 F is used as a positive electrode material, the all-solid-state battery prepared by the method has excellent cycle stability, the discharge energy density is reduced from 405Wh/kg to 373Wh/kg after 100-week cycle under the charge-discharge rate of 0.1C, and the discharge energy density retention rate is up to 93%.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an all-solid-state lithium ion battery based on an MLCC structure and a preparation method thereof.
Background
The lithium ion battery is widely applied to energy storage power systems of hydraulic power, firepower, wind power, solar power stations and the like, an uninterruptible power supply of post and telecommunications communication, and a plurality of fields of electric vehicles, military equipment, aerospace and the like. Since the energy density of the liquid lithium ion battery has been developed to the limit, the safety problem of the liquid lithium ion battery has become a limiting factor of the development. Solid lithium ion batteries are expected to solve the safety problem by using a nonflammable solid electrolyte, and have attracted wide attention at home and abroad in recent years. The good mechanical property of the solid electrolyte can inhibit the formation of lithium dendrite, and the wide electrochemical window can reduce the continuous side reaction between the metal lithium and the electrolyte, so that the use of the lithium metal negative electrode is possible, and the energy density of the lithium ion battery is greatly improved. In addition, the production process of the solid-state lithium ion battery is simpler, the shapes are more various, and the practical application is more flexible. However, the interface problems of current solid state lithium ion batteries are the major toggle problems for the electrochemical performance of solid state batteries, and these interface problems include: the chemical stability of the interface between the solid electrolyte and the anode and the lithium metal cathode, the compactness of the interface contact and the like. However, the current method of assembling the positive electrode material, the solid electrolyte and the negative electrode material into the solid lithium ion battery cannot solve the interface problem of the solid lithium ion battery.
Disclosure of Invention
The invention aims to provide a preparation method of an all-solid-state lithium ion battery based on an MLCC (multilayer ceramic capacitor) structure, which can effectively improve the energy density and the cycle stability of the solid-state battery and can ensure that the battery has higher safety.
The second purpose of the invention is to provide an all-solid-state lithium ion battery based on an MLCC (multilayer ceramic capacitor) structure, and the structural material of each part is prepared by the method.
In order to realize the purpose, the invention adopts the following technical scheme:
a preparation method of an all-solid-state lithium ion battery based on an MLCC structure comprises the following steps:
performing ball milling treatment on the positive electrode material, the conductive agent Super P and the dispersing agent, coating slurry obtained through the ball milling treatment on a carrier tape, and drying to obtain a positive electrode layer;
performing ball milling treatment on aluminum powder and a dispersing agent, and then coating the obtained slurry on one surface of the positive electrode layer to be used as a positive electrode current collector layer;
ball-milling the positive electrode active material, the solid electrolyte and the dispersing agent, and then coating the obtained slurry on the other surface of the positive electrode layer to be used as a first transition layer;
ball-milling the solid electrolyte and the dispersant, and then coating the obtained slurry on the surface of the first transition layer to be used as a solid electrolyte layer;
performing ball milling treatment on the solid electrolyte, the Li metal powder, the Li powder surface protective agent and the dispersing agent, and then coating the obtained slurry on the surface of the solid electrolyte layer to be used as a second transition layer;
performing ball milling treatment on the Li metal powder, the additive powder and the dispersing agent, and then coating the obtained slurry on the surface of the second transition layer to be used as a negative electrode layer;
performing ball milling treatment on aluminum powder and a dispersing agent, and coating the obtained slurry on the surface of the negative electrode layer to be used as a negative electrode current collector layer;
the compactness of interface contact among materials is enhanced through hot-press forming on a structure formed by a positive current collector layer, a positive electrode layer, a first transition layer, a solid electrolyte layer, a second transition layer, a negative electrode layer and a negative current collector layer, so that an all-solid-state battery monomer is obtained;
and (3) connecting all-solid-state battery monomers in series or in parallel in a lamination mode, and then performing hot-press molding to obtain the all-solid-state battery with the MLCC structure.
As a further improvement of the invention, the positive active material is LiVPO 4 F、LiFePO 4 、LiNi x Co y Mn z O 2 、LiNi x Co y Al z O 2 、LiCoO 2 、Li 2 MnO 3 And LiMn 2 O 4 Wherein x + y + z =1.
As a further improvement of the invention, the solid electrolyte is Li 7 La 3 Zr 2 O 12 、Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 And LiZr 2 (PO 4 ) 3 One or more of them.
As a further improvement of the invention, the dispersant is formed by mixing a solvent, a binder and a plasticizer; wherein the solvent is ethanol or deionized water; the adhesive is polyvinyl alcohol or ethyl cellulose; the plasticizer is turpentine, glycerol or octyl dimethyl ester.
As a further improvement of the invention, the Li powder surface protective agent is NH 4 F、NH 4 H 2 PO 4 And H 2 SiO 3 One or more of them.
As a further improvement of the invention, the additive powder is one or more of Al powder, si powder, mg powder and graphene.
As a further improvement of the invention, the thicknesses of the positive electrode current collector layer, the positive electrode layer, the first transition layer, the solid electrolyte layer, the second transition layer, the negative electrode layer and the negative electrode current collector layer are respectively 2-10 μm, 30-100 μm, 2-5 μm, 5-20 μm, 2-5 μm and 2-5 μm.
As a further improvement of the invention, the ball milling treatment is carried out in a ball mill for 5 to 20 hours.
As a further improvement of the invention, the positive electrode current collector layer, the positive electrode layer, the first transition layer, the solid electrolyte layer, the second transition layer, the negative electrode layer and the negative electrode current collector layer are dried after being prepared, and the drying condition is that the drying is carried out for 5 to 20 hours at the temperature of 50 to 100 ℃.
An all-solid-state lithium ion battery based on an MLCC structure comprises all-solid-state battery cells which are connected in series or in parallel in a lamination mode;
the all-solid-state battery monomer comprises a positive electrode current collector layer, a positive electrode layer, a first transition layer, a solid electrolyte layer, a second transition layer, a negative electrode layer and a negative electrode current collector layer which are sequentially stacked.
Compared with the prior art, the invention has the following beneficial effects:
the invention compounds the anode current collector layer, the anode layer, the transition layer formed by the anode material and the solid electrolyte, the transition layer formed by the solid electrolyte and the metal lithium cathode, the composite metal lithium cathode layer and the cathode current collector layer by the tape casting coating process, and enhances the compactness of interface contact between the materials by hot-press molding to obtain the all-solid-state battery monomer. The obtained all-solid-state battery cells are laminatedAnd connecting the batteries in series or in parallel, and then performing hot-press molding to obtain the all-solid-state battery with the MLCC structure. The invention can effectively improve the energy density and the cycling stability of the solid-state battery and can ensure that the battery has higher safety. The composite formed by mixing the electrode material and the solid electrolyte is used as a transition layer, and the buffer layer formed by an extremely thin mixture is arranged between the positive electrode, the negative electrode and the solid electrolyte of the battery, so that the active material of the battery can be fully contacted with the electrolyte, and lithium ions in the all-solid-state lithium ion battery in the charging and discharging process can be efficiently transferred, the performance of the battery can be effectively improved, and meanwhile, the safety of the battery can be effectively guaranteed. The invention can effectively improve the energy density of the solid-state battery and simultaneously can effectively ensure that the battery has higher safety. The invention greatly improves the electrochemical performance of the battery and is suitable for practical application and large-scale production. By LiVPO 4 F is used as a positive electrode material, the all-solid-state battery prepared by the method has excellent cycle stability, the discharge energy density is reduced from 405Wh/kg to 373Wh/kg after 100-week cycle under the charge-discharge rate of 0.1C, and the discharge energy density retention rate is up to 93%.
The chip multilayer Ceramic capacitor (MLCC) firstly adopts a tape casting method to prepare a Ceramic dielectric membrane, is laminated after being coated with an electrode material and is sintered into a whole, and has the characteristics of small volume and high capacity. The lithium ion solid-state battery prepared by the novel MLCC process can effectively improve the mass energy density and the volume energy density and improve the structural stability of the battery.
Drawings
Fig. 1 is a schematic view of an all-solid-state battery cell according to the present invention;
fig. 2 is a schematic diagram of the parallel connection of all-solid-state batteries according to the present invention;
fig. 3 is a schematic diagram of a series connection of all-solid-state batteries according to the present invention;
wherein, 1, a positive current collector; 2. a positive electrode layer; 3. a first transition layer; 4. a solid electrolyte layer; 5. a second transition layer; 6. a negative electrode layer; 7. a negative current collector layer;
fig. 4 is a graph of the discharge specific energy cycling stability of the all-solid-state battery described in example 1.
Detailed Description
To make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be noted that the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein, and thus the scope of the present invention is not limited by the specific embodiments disclosed below.
As shown in fig. 1 to 3, the all-solid-state lithium ion battery based on the MLCC structure of the present invention includes all-solid-state battery cells connected in series or in parallel by way of lamination;
the all-solid-state battery monomer comprises a positive current collector layer 1, a positive electrode layer 2, a first transition layer 3, a solid electrolyte layer 4, a second transition layer 5, a negative electrode layer 6 and a negative current collector layer 7 which are sequentially stacked.
A preparation method of an all-solid-state lithium ion battery based on an MLCC structure comprises the following steps:
1) And (3) performing ball milling on the positive electrode material, the conductive agent Super P and the dispersing agent in a ball mill for 5-20 hours according to a certain proportion, coating the obtained slurry on a carrier tape by adopting a casting machine, and drying to obtain the positive electrode layer. And (2) carrying out ball milling on aluminum powder and a dispersing agent in a ball mill for 5-20 hours according to a certain proportion, then coating the obtained slurry on the surface of a positive electrode to be used as a positive electrode current collector layer, and drying at 50-100 ℃ for 5-20 hours.
2) Ball-milling the positive electrode active material, the solid electrolyte and the dispersant in a ball mill for 5-20 hours according to a certain proportion, then coating the obtained slurry on the other surface of the positive electrode to be used as a first transition layer 3, and drying for 5-20 hours at 50-100 ℃. The solid electrolyte and the dispersant are ball-milled in a ball mill for 5 to 20 hours, and then the resulting slurry is coated on the surface of the first transition layer 3 as an electrolyte layer and dried at 50 to 100 ℃ for 5 to 20 hours. Ball-milling the solid electrolyte, the Li metal powder, the Li powder surface protective agent and the dispersing agent in a ball mill for 5-20 hours according to a certain proportion, then coating the obtained slurry on the surface of the solid electrolyte layer to be used as a second transition layer 5, reserving a certain blank area at one end, and drying for 5-20 hours at 50-100 ℃. And ball-milling the Li metal powder, the additive powder and the dispersing agent in a ball mill for 5-20 hours according to a certain proportion, then coating the obtained slurry on the surface of the second transition layer 5 to be used as a negative electrode layer, and drying at 50-100 ℃ for 5-20 hours. And (2) carrying out ball milling on aluminum powder and a dispersing agent in a ball mill for 5-20 hours, then coating the obtained slurry on the surface of the negative electrode layer to be used as a negative electrode current collector layer, and drying at 50-100 ℃ for 5-20 hours.
3) And 2) enhancing the compactness of the interface contact between the materials obtained in the step 2) through hot-press molding to obtain the all-solid-state battery monomer.
4) And (3) connecting the all-solid-state battery monomers obtained in the step 3) in series or in parallel in a lamination mode, and then performing hot press molding to obtain the all-solid-state battery with the MLCC structure.
Wherein the active material in the step 1) is LiVPO 4 F、LiFePO 4 、LiNi x Co y Mn z O 2 (x+y+z＝1)、LiNi x Co y Al z O 2 (x+y+z＝1)、LiCoO 2 、Li 2 MnO 3 、LiMn 2 O 4 And one or more of the anode materials.
Step 2) the solid electrolyte is Li 7 La 3 Zr 2 O 12 、Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 、LiZr 2 (PO 4 ) 3 One or more of them.
The dispersing agent is formed by mixing a solvent, a binder and a plasticizer. Wherein the solvent is ethanol or deionized water; the adhesive is polyvinyl alcohol or ethyl cellulose; the plasticizer is turpentine, glycerol or octyl dimethyl ester.
The above-mentionedThe Li powder surface protective agent is NH 4 F、NH 4 H 2 PO 4 、H 2 SiO 3 One or more of them.
The additive powder is one or more of Al powder, si powder, mg powder and graphene.
The thicknesses of the positive current collector layer 1, the positive electrode layer 2, the first transition layer 3, the electrolyte layer 3, the second transition layer 5, the negative electrode layer 6 and the negative current collector layer 7 are respectively 2-10, 30-100, 2-5, 5-20, 2-5 and 2-5 microns.
The invention discloses a preparation method of an all-solid-state lithium ion battery based on an MLCC structure. And connecting the obtained all-solid-state battery monomers in series or in parallel in a lamination mode, and then performing hot-press molding to obtain the all-solid-state battery with the MLCC structure.
The present invention will be described in detail below with reference to specific embodiments and the accompanying drawings.
Example 1
In the first step, liVPO is mixed according to the mass ratio of 9:1 4 And F, mixing the positive electrode material and the conductive agent Super P, adding a dispersing agent, carrying out ball milling in a ball mill for 10 hours, coating the obtained slurry on a carrier tape by adopting a casting machine, and drying to obtain the positive electrode layer. And (2) carrying out ball milling on aluminum powder and a dispersing agent in a ball mill for 10 hours according to a certain proportion, then coating the obtained slurry on the surface of a positive electrode to be used as a positive electrode current collector layer, and drying for 15 hours at the temperature of 60 ℃. The dispersing agent is composed of deionized water, polyvinyl alcohol and glycerol according to a volume ratio of 1.
Secondly, the anode active material and Li are mixed according to a certain proportion 7 La 3 Zr 2 O 12 And a dispersant were ball-milled in a ball mill for 10 hours, and then the resultant slurry was coated on the other surface of the positive electrode as a first transition layer 3 and dried at 60 degrees celsiusDrying is carried out for 15 hours. The solid electrolyte and the dispersant were ball-milled in a ball mill for 10 hours, and then the resulting slurry was coated on the surface of the first transition layer 3 as an electrolyte layer and dried at 60 degrees celsius for 15 hours. Mixing Li in a mass ratio of 20 7 La 3 Zr 2 O 12 Li metal powder and NH 4 And F, performing ball milling on the slurry and a dispersing agent in a ball mill for 10 hours, then coating the obtained slurry on the surface of the solid electrolyte layer to form a second transition layer 5, reserving a certain blank area at one end, and drying at 60 ℃ for 15 hours. The Li metal powder and the additive powder, and the dispersant were ball-milled in a ball mill for 10 hours at a mass ratio of 95. And (3) carrying out ball milling on aluminum powder and a dispersing agent in a ball mill for 10 hours, then coating the obtained slurry on the surface of the negative electrode layer to be used as a negative electrode current collector layer, and drying at 60 ℃ for 15 hours. The dispersing agent is composed of deionized water, polyvinyl alcohol and glycerol according to a volume ratio of 1.
Thirdly, the compactness of interface contact between the materials is enhanced through hot-press molding of the obtained materials, and the all-solid-state battery monomer is obtained.
And fourthly, connecting 5 monomers in series in the all-solid-state battery monomer obtained in the third step in a lamination mode, and then performing hot press molding to obtain the all-solid-state battery with the MLCC structure.
The all-solid-state battery having the MLCC structure obtained in this example 1 was subjected to a cycle performance test. Fig. 4 is a cycle performance of the all-solid battery under the charge-discharge rate condition of 0.1C. As can be seen from FIG. 4, the discharge energy density decreased from 405Wh/kg to 373Wh/kg after 100-week cycles, and the discharge energy density retention was as high as 93%.
Example 2
In the first step, liVPO is mixed according to the mass ratio of 8:2 4 And F, mixing the positive electrode material and the conductive agent Super P, adding a dispersing agent, carrying out ball milling in a ball mill for 10 hours, coating the obtained slurry on a carrier tape by adopting a casting machine, and drying to obtain the positive electrode layer. Aluminum powder and a dispersant are ball-milled for 10 hours in a ball mill according to a certain proportion, and thenThe resulting slurry was coated on the surface of a positive electrode as a positive electrode current collector layer, and dried at 60 degrees celsius for 15 hours. The dispersing agent is composed of deionized water, polyvinyl alcohol and glycerol according to a volume ratio of 1.
Secondly, the anode active material and Li are mixed according to a certain proportion 7 La 3 Zr 2 O 12 And a dispersant were ball-milled in a ball mill for 10 hours, and then the resultant slurry was coated on the other side of the positive electrode as a first transition layer 3 and dried at 80 degrees celsius for 10 hours. The solid electrolyte and the dispersant were ball-milled in a ball mill for 15 hours, and then the resulting slurry was coated on the surface of the first transition layer 3 as an electrolyte layer and dried at 80 degrees celsius for 9 hours. Mixing Li in a mass ratio of 20 7 La 3 Zr 2 O 12 Li metal powder and NH 4 And F, ball-milling the slurry and a dispersing agent in a ball mill for 15 hours, then coating the obtained slurry on the surface of the solid electrolyte layer to be used as a second transition layer 5, reserving a certain blank area at one end, and drying at 50 ℃ for 20 hours. The Li metal powder, the additive powder and the dispersant were ball-milled in a ball mill for 6 hours at a mass ratio of 95. And (3) carrying out ball milling on aluminum powder and a dispersing agent in a ball mill for 20 hours, then coating the obtained slurry on the surface of the negative electrode layer to be used as a negative electrode current collector layer, and drying at 100 ℃ for 5 hours. The dispersing agent is composed of deionized water, polyvinyl alcohol and glycerol according to a volume ratio of 1.
And thirdly, the compactness of the interface contact between the materials is enhanced through hot-press molding of the obtained materials, and the all-solid-state battery monomer is obtained.
And fourthly, connecting 5 monomers in series in the all-solid-state battery monomer obtained in the third step in a lamination mode, and then performing hot press molding to obtain the all-solid-state battery with the MLCC structure.
Example 3
In the first step, liVPO is mixed according to the mass ratio of 8.5 4 Mixing the F anode material and the conductive agent Super P, adding a dispersing agent, carrying out ball milling for 5 hours in a ball mill, and adopting tape castingAnd coating the obtained slurry on a carrier tape, and drying to obtain the positive electrode layer. Aluminum powder and a dispersing agent are ball-milled in a ball mill for 12 hours according to a certain proportion, then the obtained slurry is coated on the surface of a positive electrode to be used as a positive electrode current collecting layer, and the positive electrode current collecting layer is dried for 20 hours at 50 ℃. The dispersing agent is composed of deionized water, polyvinyl alcohol and glycerol according to a volume ratio of 1.
Secondly, the anode active material and Li are mixed according to a certain proportion 7 La 3 Zr 2 O 12 And a dispersant were ball-milled in a ball mill for 10 hours, and then the resultant slurry was coated on the other side of the positive electrode as a first transition layer 3 and dried at 60 degrees celsius for 15 hours. The solid electrolyte and the dispersant were ball-milled in a ball mill for 10 hours, and then the resulting slurry was coated on the surface of the first transition layer 3 as an electrolyte layer and dried at 60 degrees celsius for 15 hours. Mixing Li in a mass ratio of 20 7 La 3 Zr 2 O 12 Li metal powder and NH 4 And F, ball-milling the slurry and a dispersing agent in a ball mill for 10 hours, then coating the obtained slurry on the surface of the solid electrolyte layer to be used as a second transition layer 5, reserving a certain blank area at one end, and drying at 60 ℃ for 15 hours. The Li metal powder and the additive powder and the dispersant were ball-milled in a ball mill at a mass ratio of 95. And (3) carrying out ball milling on aluminum powder and a dispersing agent in a ball mill for 10 hours, then coating the obtained slurry on the surface of the negative electrode layer to be used as a negative electrode current collector layer, and drying at 60 ℃ for 15 hours. The dispersing agent is composed of deionized water, polyvinyl alcohol and glycerol according to a volume ratio of 1.
And thirdly, the compactness of the interface contact between the materials is enhanced through hot-press molding of the obtained materials, and the all-solid-state battery monomer is obtained.
And fourthly, 5 monomers are connected in series in the all-solid-state battery monomer obtained in the third step in a laminating mode, and then hot-press molding is carried out to obtain the all-solid-state battery with the MLCC structure.
Example 4
First step ofLiVPO was mixed at a mass ratio of 7:3 4 And F, mixing the positive electrode material and the conductive agent Super P, adding a dispersing agent, carrying out ball milling in a ball mill for 10 hours, coating the obtained slurry on a carrier tape by using a casting machine, and drying to obtain the positive electrode layer. And (2) performing ball milling on aluminum powder and a dispersing agent in a ball mill for 10 hours according to a certain proportion, then coating the obtained slurry on the surface of a positive electrode to be used as a positive electrode current collector layer, and drying at 60 ℃ for 15 hours. The dispersing agent is composed of deionized water, polyvinyl alcohol and glycerol according to a volume ratio of 1.
Secondly, the anode active material and Li are mixed according to a certain proportion 7 La 3 Zr 2 O 12 And a dispersant were ball-milled in a ball mill for 10 hours, and then the resultant slurry was coated on the other side of the positive electrode as a first transition layer 3 and dried at 60 degrees celsius for 15 hours. The solid electrolyte and the dispersant were ball-milled in a ball mill for 10 hours, and then the resulting slurry was coated on the surface of the first transition layer 3 as an electrolyte layer and dried at 60 degrees celsius for 15 hours. Mixing Li in a mass ratio of 20 7 La 3 Zr 2 O 12 Li metal powder and NH 4 And F, ball-milling the slurry and a dispersing agent in a ball mill for 16 hours, then coating the obtained slurry on the surface of the solid electrolyte layer to be used as a second transition layer 5, reserving a certain blank area at one end, and drying at 80 ℃ for 10 hours. The Li metal powder, the additive powder and the dispersant were ball-milled in a ball mill for 5 hours at a mass ratio of 95. And (3) carrying out ball milling on aluminum powder and a dispersing agent in a ball mill for 20 hours, then coating the obtained slurry on the surface of the negative electrode layer to be used as a negative electrode current collector layer, and drying at 70 ℃ for 20 hours. The dispersing agent is composed of deionized water, polyvinyl alcohol and glycerol according to a volume ratio of 1.
And thirdly, the compactness of the interface contact between the materials is enhanced through hot-press molding of the obtained materials, and the all-solid-state battery monomer is obtained.
And fourthly, 5 monomers are connected in series in the all-solid-state battery monomer obtained in the third step in a laminating mode, and then hot-press molding is carried out to obtain the all-solid-state battery with the MLCC structure.
All articles and references disclosed above, including patent applications and publications, are hereby incorporated by reference for all purposes. The term "consisting essentially of …" describing a combination shall include the identified elements, components, parts or steps as well as other elements, components, parts or steps that do not materially affect the basic novel characteristics of the combination. The use of the terms "comprising" or "including" to describe combinations of elements, components, or steps herein also contemplates embodiments that consist essentially of such elements, components, or steps. By using the term "may" herein, it is intended to indicate that any of the described attributes that "may" include are optional.
A plurality of elements, components, parts or steps can be provided by a single integrated element, component, part or step. Alternatively, a single integrated element, component, part or step may be divided into separate plural elements, components, parts or steps. The disclosure of "a" or "an" to describe an element, ingredient, component or step is not intended to foreclose other elements, ingredients, components or steps.
It is to be understood that the above description is intended to be illustrative, and not restrictive. Many embodiments and many applications other than the examples provided would be apparent to those of skill in the art upon reading the above description. The scope of the present teachings should, therefore, be determined not with reference to the above description, but should instead be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are hereby incorporated by reference for all purposes. The omission in the foregoing claims of any aspect of subject matter that is disclosed herein is not a disclaimer of such subject matter, nor is it to be construed that applicant does not consider such subject matter to be part of the disclosed inventive subject matter.
Claims (4)
1. A preparation method of an all-solid-state lithium ion battery based on an MLCC structure is characterized by comprising the following steps:
performing ball milling treatment on the positive electrode material, the conductive agent Super P and the dispersing agent, coating slurry obtained through the ball milling treatment on a carrier tape, and drying to obtain a positive electrode layer;
performing ball milling treatment on aluminum powder and a dispersing agent, and then coating the obtained slurry on one surface of the positive electrode layer to be used as a positive electrode current collector layer;
ball-milling the positive electrode active material, the solid electrolyte and the dispersing agent, and then coating the obtained slurry on the other surface of the positive electrode layer to be used as a first transition layer;
performing ball milling treatment on the solid electrolyte and the dispersing agent, and then coating the obtained slurry on the surface of the first transition layer to be used as a solid electrolyte layer;
performing ball milling treatment on the solid electrolyte, li metal powder, a Li powder surface protective agent and a dispersing agent, and then coating the obtained slurry on the surface of the solid electrolyte layer to be used as a second transition layer;
performing ball milling treatment on the Li metal powder, the additive powder and the dispersing agent, and then coating the obtained slurry on the surface of the second transition layer to be used as a negative electrode layer;
performing ball milling treatment on aluminum powder and a dispersing agent, and coating the obtained slurry on the surface of the negative electrode layer to be used as a negative electrode current collector layer;
the compactness of interface contact among materials is enhanced through hot-press forming on a structure formed by a positive current collector layer, a positive electrode layer, a first transition layer, a solid electrolyte layer, a second transition layer, a negative electrode layer and a negative current collector layer, so that an all-solid-state battery monomer is obtained;
all-solid-state battery monomers are connected in series or in parallel in a lamination mode, and then hot-press molding is carried out to obtain an all-solid-state battery with an MLCC structure;
the positive active material is LiVPO 4 F、LiFePO 4 、LiNi x Co y Mn z O 2 、LiNi x Co y Al z O 2 、LiCoO 2 、Li 2 MnO 3 And LiMn 2 O 4 Wherein x + y + z =1;
the solid electrolyte is Li 7 La 3 Zr 2 O 12 、Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 And LiZr 2 (PO 4 ) 3 One or more of the above;
the dispersing agent is formed by mixing a solvent, a bonding agent and a plasticizer; wherein the solvent is ethanol or deionized water; the adhesive is polyvinyl alcohol or ethyl cellulose; the plasticizer is turpentine, glycerol or octyl dimethyl ester;
the thicknesses of the positive electrode current collector layer, the positive electrode layer, the first transition layer, the solid electrolyte layer, the second transition layer, the negative electrode layer and the negative electrode current collector layer are respectively 2-10 mu m, 30-100 mu m, 2-5 mu m, 5-20 mu m, 2-5 mu m and 2-5 mu m;
drying the positive current collector layer, the positive electrode layer, the first transition layer, the solid electrolyte layer, the second transition layer, the negative electrode layer and the negative current collector layer after preparation, wherein the drying condition is 50-100 ℃;
the Li powder surface protective agent is NH 4 F；
The additive powder is one or more of Al powder, si powder, mg powder and graphene.
2. The method for preparing an all-solid-state lithium ion battery based on the MLCC structure of claim 1, wherein the ball milling treatment time is 5-20 hours.
3. The method for preparing an all-solid-state lithium ion battery based on the MLCC structure of claim 1, wherein the drying time is 5-20 hours.
4. An all-solid-state lithium ion battery based on an MLCC structure, which is prepared by the method of any one of claims 1 to 3 and comprises all-solid-state battery cells connected in series or in parallel in a lamination mode;
the all-solid-state battery monomer comprises a positive electrode current collector layer, a positive electrode layer, a first transition layer, a solid electrolyte layer, a second transition layer, a negative electrode layer and a negative electrode current collector layer which are sequentially stacked.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101315993A (en) * | 2007-05-28 | 2008-12-03 | 东莞新能源电子科技有限公司 | Method for manufacturing stack type lithium ion battery |
| CN101969111A (en) * | 2010-09-30 | 2011-02-09 | 湛江市聚鑫新能源有限公司 | Silicon-carbon alloy cathode material for lithium ion batteries and preparation method thereof |
| CN202871918U (en) * | 2012-08-08 | 2013-04-10 | 安阳金钟新能源有限公司 | Lithium ion battery with wide temperature zone |
| CN104882635A (en) * | 2015-05-30 | 2015-09-02 | 深圳市格瑞普电池有限公司 | Laminated lithium ion battery, battery pack comprising same and pole piece of laminated lithium ion battery |
| CN106450169A (en) * | 2016-08-31 | 2017-02-22 | 湖北宇电能源科技股份有限公司 | Manufacturing method of negative plate of safety lithium-ion battery |
| CN110556568A (en) * | 2019-09-27 | 2019-12-10 | 安徽坤宇塑金新能源技术有限公司 | high-voltage monomer solid-state lithium ion battery and preparation method thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5310996B2 (en) * | 2008-04-18 | 2013-10-09 | 住友電気工業株式会社 | Lithium battery |
| CN102456929B (en) * | 2011-07-20 | 2014-10-08 | 宁波大学 | Method for manufacturing lithium iron phosphate all-solid-state film cell by in-situ spray pyrolysis |
| CN106876668A (en) * | 2016-11-21 | 2017-06-20 | 蔚来汽车有限公司 | Combination electrode material of solid state lithium battery and preparation method thereof |
| JP6933250B2 (en) * | 2017-03-28 | 2021-09-08 | 株式会社村田製作所 | All-solid-state batteries, electronic devices, electronic cards, wearable devices and electric vehicles |
| CN108232318B (en) * | 2018-01-30 | 2020-07-17 | 陕西煤业化工技术研究院有限责任公司 | Manufacturing method of all-solid-state power lithium ion battery |
| JP7154847B2 (en) * | 2018-07-06 | 2022-10-18 | Fdk株式会社 | Method for manufacturing all-solid-state battery |
| CN109065945A (en) * | 2018-08-17 | 2018-12-21 | 西安交通大学 | A kind of solid electrolyte membrane and its preparation method and application |
| CN109768318A (en) * | 2019-03-12 | 2019-05-17 | 浙江锋锂新能源科技有限公司 | A kind of mixing solid-liquid electrolyte lithium battery |
| CN110380133A (en) * | 2019-08-02 | 2019-10-25 | 中南大学 | A kind of transition zone design method of inorganic solid electrolyte and positive interpolar |
-
2020
- 2020-10-09 CN CN202011073823.9A patent/CN112186262B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101315993A (en) * | 2007-05-28 | 2008-12-03 | 东莞新能源电子科技有限公司 | Method for manufacturing stack type lithium ion battery |
| CN101969111A (en) * | 2010-09-30 | 2011-02-09 | 湛江市聚鑫新能源有限公司 | Silicon-carbon alloy cathode material for lithium ion batteries and preparation method thereof |
| CN202871918U (en) * | 2012-08-08 | 2013-04-10 | 安阳金钟新能源有限公司 | Lithium ion battery with wide temperature zone |
| CN104882635A (en) * | 2015-05-30 | 2015-09-02 | 深圳市格瑞普电池有限公司 | Laminated lithium ion battery, battery pack comprising same and pole piece of laminated lithium ion battery |
| CN106450169A (en) * | 2016-08-31 | 2017-02-22 | 湖北宇电能源科技股份有限公司 | Manufacturing method of negative plate of safety lithium-ion battery |
| CN110556568A (en) * | 2019-09-27 | 2019-12-10 | 安徽坤宇塑金新能源技术有限公司 | high-voltage monomer solid-state lithium ion battery and preparation method thereof |
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