CN112331913A - Composite solid electrolyte, preparation method and application - Google Patents
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Abstract
The invention provides a composite solid electrolyte, a preparation method and application, wherein the composite solid electrolyte comprises a first solid electrolyte layer and a second solid electrolyte layer, wherein the first solid electrolyte layer comprises an organic polymer A, lithium salt and a modified nano inorganic solid electrolyte; the second solid electrolyte layer includes an organic polymer B, a lithium salt, nanodiamonds, graphene, and a dispersant. The design of the invention fully considers the technical requirements of the anode and the cathode, and realizes the consideration of high voltage resistance, lithium dendrite inhibition and cathode volume expansion while ensuring high ionic conductivity. The electrolyte membrane can effectively inhibit the generation of lithium dendrites of the solid lithium battery, and improve the energy density, cycle life and safety performance of the solid lithium battery.
Description
Technical Field
The invention relates to the technical field of energy storage batteries, in particular to a composite solid electrolyte, a preparation method and application.
Background
With the rapid development of new energy automobiles, more stringent requirements are put forward on the energy density, safety and the like of batteries. The liquid electrolyte adopted in the current main flow power battery has certain potential safety hazard due to the characteristics of easy leakage and flammability, and the solid-state battery is expected to be applied to the fields of electric automobiles, consumer electronic equipment and the like as a next-generation high-performance electrochemical energy storage device due to the consideration of energy density and safety performance.
The solid electrolyte is a core component of the solid lithium battery, and the development of the solid electrolyte with high ionic conductivity, wide electrochemical window, good electrode interface, effective inhibition of lithium dendrite and other good comprehensive properties is the key of the solid battery development. At present, solid electrolytes can be classified into inorganic solid electrolytes and organic polymer electrolytes. The inorganic solid electrolyte has the main advantages of high ion conductivity, good stability and high transference number of lithium ions at room temperature, but the solid-solid contact capability between the inorganic solid electrolyte and a battery electrode is poor, so that the large-scale application of the inorganic solid electrolyte is restricted. Compared with the prior art, the organic polymer electrolyte has the advantage of easy deformation due to elasticity, can effectively improve the interface contact between an electrode and the electrolyte, and has the problems of low room-temperature ionic conductivity and narrow electrochemical window. Researchers in the field prepare the organic-inorganic composite solid electrolyte by fusing the organic polymer electrolyte and the inorganic solid electrolyte, and combine the advantages of the organic polymer electrolyte and the inorganic solid electrolyte to improve the comprehensive performance.
The patent application with publication number CN108336398A discloses an organic/inorganic composite electrolyte and a preparation method thereof, wherein the organic/inorganic composite electrolyte is prepared by mixing an inorganic solid electrolyte, a polymer matrix and an organic solvent, and then sequentially casting to form a film and drying to obtain an inorganic/organic composite solid electrolyte film. The electrolyte obtained in the patent integrates the advantages of organic and inorganic electrolytes, has good flexibility and high conductivity, but a composite electrolyte membrane obtained by simply mixing the organic and inorganic electrolytes still cannot meet the comprehensive performance requirements of a solid-state battery, is particularly difficult to simultaneously meet the requirements of stable contact with metal lithium, can resist the penetration of lithium dendrites, and can bear high voltage and match with a high-voltage positive electrode material, thereby greatly limiting the application of the electrolyte in the solid-state battery, particularly the solid-state battery taking the metal lithium as a negative electrode.
Disclosure of Invention
The invention provides a composite solid electrolyte, a preparation method and application thereof, and a solid battery which can inhibit lithium dendrites and realize high voltage is prepared. The battery has higher voltage, higher specific capacity and cycling stability, and the structural design can inhibit the growth of metallic lithium dendrites and improve the safety of the battery. The solid-state battery has the advantages of simple preparation method, low cost, excellent electrochemical performance and wide application prospect and advantages.
The technical scheme for realizing the invention is as follows:
a composite solid electrolyte comprising a first solid electrolyte layer and a second solid electrolyte layer, the first solid electrolyte layer comprising an organic polymer a, a lithium salt and a modified nano-inorganic solid electrolyte; the second solid electrolyte layer includes an organic polymer B, a lithium salt, nanodiamonds, graphene, and a dispersant.
The weight percentages of the components in the first solid electrolyte layer are respectively as follows: 20-80% of organic polymer A, 10-30% of lithium salt and 1-60% of modified nano inorganic solid electrolyte.
The conductivity of the modified nano inorganic solid electrolyte is 1 multiplied by 10-5S/cm~1×10-1S/cm, and the particle size of the modified nano inorganic solid electrolyte is 10-200 nm.
The organic polymer A is one or more than two of polyvinylidene fluoride, polyvinylidene fluoride copolymer and polyacrylonitrile; the lithium salt is LiClO4、LiPF6、LiBF4、LiN(SO2CF3)2And LiN (SO)2CF2CF3)2One or more of; the modified nano inorganic solid electrolyte is obtained by grafting and modifying one or more of LLTO, LLZO or LATP by a coupling agent.
The coupling agent accounts for 0.5-20% of the mass of the modified nano inorganic solid electrolyte.
The coupling agent is a silane coupling agent, preferably (3-chloropropyl) trimethoxysilane; one or more of bis (2-hydroxyethyl) -3-aminopropyl-methoxysilane and triethoxysilylcarbinol.
The second solid electrolyte layer comprises the following components in percentage by weight: 20-80% of organic polymer B, 10-30% of lithium salt, 1-50% of nano diamond, 1-50% of graphene and 0.05-5% of dispersing agent.
The organic polymer B is polyoxyethylene, the particle size distribution of the nano-diamond is 1-50nm, and preferably, the particle size is 5-20 nm; the lithium salt is LiClO4、LiPF6、LiBF4、LiN(SO2CF3)2And LiN (SO)2CF2CF3)2One or more of; the graphene is selected from one or more of single-layer graphene, double-layer graphene and few-layer graphene with 3-10 layers, and the diameter distribution of the graphene is 1-50 mu m; the dispersant is sodium dodecyl benzene sulfonate.
The total thickness of the first solid electrolyte layer and the second solid electrolyte layer is 10-100 μm, and the thickness of the first solid electrolyte layer is 5-80 μm, preferably 17-55 μm; the thickness of the second solid electrolyte layer is 5-40 μm, preferably 7-15 μm.
The preparation method of the composite solid electrolyte comprises the following steps:
(1) dispersing inorganic solid electrolyte into an ethanol solution to obtain a mixed solution with the mass concentration of 1-10%, adding a silane coupling agent accounting for 0.5-20% of the mass of the inorganic solid electrolyte, and heating at 40-80 ℃ for 12h to fully react;
(2) after the reaction liquid in the step (1) is subjected to high-speed centrifugal separation, washing with ethanol for 2-3 times, taking out a precipitate, and drying in vacuum to obtain a modified inorganic solid electrolyte;
(3) dissolving an organic polymer A and lithium salt in a solvent, and uniformly stirring to obtain a mixed solution; the solvent is selected from one or a combination of more of Dimethylformamide (DMF), Dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO) and N-methyl-2-pyrrolidone (NMP);
(4) adding a solid electrolyte of a modifying machine into the mixed solution obtained in the step (3), continuously stirring to prepare a first slurry, coating the first slurry on a base material, and drying to form a first solid electrolyte layer; the drying method comprises baking at 25-120 deg.C for 0.1-12 hr;
(5) mixing an organic polymer B, a lithium salt, nano-diamond, graphene, a dispersing agent and a solvent to prepare a second slurry, and forming a second solid electrolyte layer on the first solid electrolyte layer to obtain the composite solid electrolyte.
Preferably, the method of forming the second solid electrolyte layer in step (5) is: and directly coating the second slurry on the first solid electrolyte layer, and drying to form a second solid electrolyte layer.
Preferably, in the method of forming the second solid electrolyte layer in step (5), the drying is performed by baking at 25 to 60 ℃ for 0.1 to 12 hours.
In the step (1), the mass concentration of the inorganic solid electrolyte after being dispersed into the ethanol solution is 1-10%, the mass of the added silane coupling agent is 0.5-20% of the mass of the inorganic solid electrolyte, the heating temperature is 40-80 ℃, and the time is 12 hours.
The invention provides a solid-state lithium battery, which comprises a positive electrode, a metallic lithium negative electrode and the solid-state electrolyte of the first aspect, wherein the second electrolyte layer is close to the lithium metallic negative electrode; the first electrolyte layer is adjacent to the positive electrode.
In the all solid-state lithium metal battery of the present invention, the positive electrode includes a positive electrode current collector and a positive electrode membrane including a positive electrode active material, a conductive agent, and a binder, which is disposed on at least one surface of the positive electrode current collector. The lithium metal negative electrode includes a negative electrode current collector and lithium metal disposed on at least one surface of the negative electrode current collector. The specific type and composition of the positive pole piece are not particularly limited and can be selected according to actual requirements.
The preparation method of the solid-state lithium ion battery is not particularly limited, and for example, materials of all layers can be stacked in sequence and then subjected to hot-pressing compounding to form the solid-state lithium ion battery.
The solid-state battery may be a quasi-solid-state battery or a semi-solid-state battery containing a liquid, or may be an all-solid-state battery.
The invention has the beneficial effects that: the composite solid electrolyte membrane comprises a first solid electrolyte layer positioned on the positive electrode side and a second electrolyte layer positioned on the negative electrode side, wherein the first solid electrolyte layer positioned on the positive electrode side is used for compounding organic electrolyte with high oxidation potential, such as polyvinylidene fluoride, polyvinylidene fluoride copolymer, polyacrylonitrile and the like, with inorganic solid electrolyte, so that the composite solid electrolyte membrane can bear higher voltage and improve lithium ion conductivity; the second solid electrolyte layer located on the negative electrode side contains the nanodiamond material, and carbon atoms in the nanodiamond are bonded by sp3 bonds, so that the conductive material bonded by sp2 bonds or amorphous carbon is higher in chemical stability, excellent in structural stability and small in volume expansion, and can better inhibit lithium dendrites and relieve negative electrode volume expansion. The design of the composite electrolyte membrane fully considers the technical requirements of the anode and the cathode, and realizes the consideration of high pressure resistance, lithium dendrite inhibition and cathode volume expansion while ensuring high ionic conductance. The electrolyte membrane can effectively inhibit the generation of lithium dendrites of the solid lithium battery, and improve the energy density, cycle life and safety performance of the solid lithium battery.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic structural view of a solid lithium battery comprising a bi-layer solid electrolyte according to the present invention.
Wherein, 1-negative electrode; 2-positive electrode; 3-a first electrolyte layer; 4-a second electrolyte layer.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The present embodiment provides a composite electrolyte, which has a structure as shown in fig. 1, and includes: a first solid electrolyte layer 3 and a second solid electrolyte layer 4 disposed on the first solid electrolyte layer 3 side;
the material of the first solid electrolyte layer 3 is a mixture of an organic polymer A, lithium salt and modified nano inorganic solid electrolyte;
the material of the second solid electrolyte layer 4 is a mixture of an organic polymer B, lithium salt, nano-diamond, graphene and a dispersing agent;
the materials, proportions and coating thicknesses of the respective layers are shown in Table 1.
The preparation method of the composite solid electrolyte comprises the following steps:
(1) preparing a modified nano inorganic solid electrolyte:
a. dispersing a nano inorganic solid electrolyte into an ethanol solution to obtain a mixed solution with the mass concentration of 1-10%, adding a silane coupling agent accounting for 2% of the mass of the inorganic filler, uniformly stirring, and heating at 60 ℃ for 12 hours;
b. after the reaction liquid is subjected to high-speed centrifugal separation, washing with ethanol for 2-3 times, taking out the precipitate, and putting the precipitate into a drying oven for vacuum drying to obtain a modified inorganic solid electrolyte;
c. dissolving a polymer matrix and lithium salt in a solvent, and uniformly stirring to obtain a mixed solution;
(2) preparing a composite solid electrolyte:
mixing the material with the first solid electrolyte layer with acetonitrile serving as a solvent to prepare first slurry, coating the first slurry on a release film, and baking the release film for 30min at 55 ℃ to form the first solid electrolyte layer;
(2) and mixing the material of the second solid electrolyte layer with acetonitrile serving as a solvent to prepare second slurry, coating the second slurry on the first solid electrolyte layer, and baking the first solid electrolyte layer at 55 ℃ for 20min to obtain the composite solid electrolyte.
Preparing a solid lithium ion battery:
(1) preparation of positive pole piece
LiNi serving as a positive electrode active material1/3Co1/3Mn1/3O2Mixing an electrolyte material LTFSI, a conductive agent Super-P and a binder PVDF according to a mass ratio of 70:24:3:3, adding a solvent NMP, and stirring under the action of a vacuum stirrer until the system is uniform to obtain anode slurry; and uniformly coating the positive electrode slurry on two surfaces of the positive electrode current collector aluminum foil, airing at room temperature, transferring to an oven for continuous drying, and then performing cold pressing and slitting to obtain the positive electrode piece.
(2) Preparation of lithium metal negative pole piece
And (3) rolling and attaching the lithium foil to two surfaces of the copper foil of the negative current collector, and then slitting to obtain the negative pole piece.
And sequentially laminating the positive pole piece, the composite electrolyte layer and the lithium metal negative pole prepared by the preparation method, and pressurizing under 200MPa to prepare the all-solid-state lithium ion battery. The composite electrolyte membrane has a first electrolyte layer 3 facing the positive electrode 2 and a second electrolyte layer 4 facing the negative electrode 1, and the specific structure is shown in fig. 1.
Examples 2 to 10
Examples 2 to 10 each provide a composite solid electrolyte differing from example 1 in the materials and proportions of the layers, as shown in table 1.
Comparative examples 1 to 2
Comparative examples 1-2 differ from example 1 in the materials and proportions of the layers, as shown in table 1.
All solid-state lithium metal batteries of examples 1 to 10 and comparative examples 1 to 2 were tested according to the items in table 2, a multimeter was used for internal resistance test, and a novyi charge-discharge meter was used for specific capacity, first efficiency and cycle life test.
As can be seen from the test results in table 2, the solid-state batteries of examples can significantly reduce the internal resistance of the solid-state battery, and improve the discharge capacity and cycle performance, as compared to the comparative examples.
Table 1 results of performance test of examples and comparative examples
Table 2 results of performance test of examples and comparative examples
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A composite solid electrolyte characterized by: the electrolyte comprises a first solid electrolyte layer and a second solid electrolyte layer, wherein the first solid electrolyte layer comprises an organic polymer A, a lithium salt and a modified nano inorganic solid electrolyte; the second solid electrolyte layer includes an organic polymer B, a lithium salt, nanodiamonds, graphene, and a dispersant.
2. The composite solid-state electrolyte of claim 1, wherein: the weight percentages of the components in the first solid electrolyte layer are respectively as follows: 20-80% of organic polymer A, 10-30% of lithium salt and 1-60% of modified nano inorganic solid electrolyte.
3. The composite solid-state electrolyte of claim 1, wherein: the conductivity of the modified nano inorganic solid electrolyte is 1 multiplied by 10-5S/cm~1×10-1S/cm, and the particle size of the modified nano inorganic solid electrolyte is 10-200 nm.
4. The composite solid-state electrolyte of claim 2, wherein: the organic polymer A is one or more than two of polyvinylidene fluoride, polyvinylidene fluoride copolymer and polyacrylonitrile; the lithium salt is LiClO4、LiPF6、LiBF4、LiN(SO2CF3)2And LiN (SO)2CF2CF3)2One or more of; the modified nano inorganic solid electrolyte is obtained by grafting and modifying one or more of LLTO, LLZO or LATP by a coupling agent.
5. The composite solid-state electrolyte of claim 1, wherein: the second solid electrolyte layer comprises the following components in percentage by weight: 20-80% of organic polymer B, 10-30% of lithium salt, 1-50% of nano diamond, 1-50% of graphene and 0.05-5% of dispersing agent.
6. The composite solid-state electrolyte of claim 5, wherein: the organic polymer B is polyoxyethylene, the particle size distribution of the nano-diamond is 1-50nm, and the lithium salt is LiClO4、LiPF6、LiBF4、LiN(SO2CF3)2And LiN (SO)2CF2CF3)2One or more of; the graphene is selected from one or more of single-layer graphene, double-layer graphene and few-layer graphene with 3-10 layers, and the diameter distribution of the graphene is 1-50 mu m; the dispersant is sodium dodecyl benzene sulfonate.
7. The composite solid-state electrolyte of claim 1, wherein: the total thickness of the first solid electrolyte layer and the second solid electrolyte layer is 10-100 μm, the thickness of the first solid electrolyte layer is 5-80 μm, and the thickness of the second solid electrolyte layer is 5-40 μm.
8. The method for producing a composite solid electrolyte according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) dispersing inorganic solid electrolyte into an ethanol solution, adding a silane coupling agent, uniformly stirring, and heating for reaction;
(2) after the reaction liquid in the step (1) is subjected to high-speed centrifugal separation, washing with ethanol for 2-3 times, taking out a precipitate, and drying in vacuum to obtain a modified inorganic solid electrolyte;
(3) dissolving an organic polymer A and lithium salt in a solvent, and uniformly stirring to obtain a mixed solution;
(4) adding a solid electrolyte of a modifying machine into the mixed solution obtained in the step (3), continuously stirring to prepare a first slurry, coating the first slurry on a base material, and drying to form a first solid electrolyte layer;
(5) mixing an organic polymer B, a lithium salt, nano-diamond, graphene, a dispersing agent and a solvent to prepare a second slurry, and forming a second solid electrolyte layer on the first solid electrolyte layer to obtain the composite solid electrolyte.
9. The method for producing a composite solid electrolyte according to claim 8, characterized in that: in the step (1), the mass concentration of the inorganic solid electrolyte after being dispersed into the ethanol solution is 1-10%, the mass of the added silane coupling agent is 0.5-20% of the mass of the inorganic solid electrolyte, the heating temperature is 40-80 ℃, and the time is 12 hours.
10. Use of the composite solid electrolyte prepared by the preparation method according to claim 9 in a solid-state battery, wherein: the first solid electrolyte layer is arranged close to the anode, and the second solid electrolyte layer is arranged close to the cathode.
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| CN112864458A (en) * | 2021-03-12 | 2021-05-28 | 合肥国轩高科动力能源有限公司 | Double-layer composite solid electrolyte material and preparation method and application thereof |
| CN112864458B (en) * | 2021-03-12 | 2022-06-03 | 合肥国轩高科动力能源有限公司 | Double-layer composite solid electrolyte material and preparation method and application thereof |
| CN114142161A (en) * | 2021-11-26 | 2022-03-04 | 吉林大学 | Preparation method of modified lithium ion battery diaphragm |
| CN114142161B (en) * | 2021-11-26 | 2023-09-22 | 吉林大学 | Preparation method of modified lithium ion battery diaphragm |
| CN114156482A (en) * | 2021-12-02 | 2022-03-08 | 吉林大学 | Preparation method of nano-diamond electrolyte and nano-diamond solid electrolyte interface |
| CN114156482B (en) * | 2021-12-02 | 2023-11-17 | 吉林大学 | Preparation method of nano-diamond electrolyte and nano-diamond solid electrolyte interface |
| CN115347322A (en) * | 2022-08-30 | 2022-11-15 | 新乡市中科膜材料科技有限公司 | Preparation method and application of porous polyolefin composite membrane |
| CN115347322B (en) * | 2022-08-30 | 2024-02-02 | 新乡市中科膜材料科技有限公司 | Preparation method and application of porous polyolefin composite membrane |
| CN115371854A (en) * | 2022-09-20 | 2022-11-22 | 南京工业职业技术大学 | AC impedance spectrum type pressure sensor with composite structure |
| RU2796634C1 (en) * | 2022-10-19 | 2023-05-29 | Федеральное государственное бюджетное учреждение науки Институт химии твердого тела и механохимии Сибирского отделения Российской академии наук | Composite solid electrolyte based on ionic organic salts of substituted ammonium with butyl and methyl radicals and a heterogeneous addition of nanodiamonds |
| CN116666738A (en) * | 2023-08-02 | 2023-08-29 | 河北科技大学 | Solid electrolyte for sodium ion battery and preparation method thereof |
| CN116666738B (en) * | 2023-08-02 | 2023-09-29 | 河北科技大学 | Solid electrolyte for sodium ion battery and preparation method thereof |
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