CN116154276A - Structure battery based on solid-state battery cell, structure battery pack comprising structure battery cell and manufacturing method of structure battery pack - Google Patents

Structure battery based on solid-state battery cell, structure battery pack comprising structure battery cell and manufacturing method of structure battery pack Download PDF

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Publication number
CN116154276A
CN116154276A CN202310144346.8A CN202310144346A CN116154276A CN 116154276 A CN116154276 A CN 116154276A CN 202310144346 A CN202310144346 A CN 202310144346A CN 116154276 A CN116154276 A CN 116154276A
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solid
battery
electrolyte membrane
solid electrolyte
structural
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傅宇
李岩
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Tongji University
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Tongji University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a structural battery based on a solid-state battery core, a structural battery pack containing the same and a manufacturing method of the structural battery pack. The structural battery comprises the solid-state battery core and an encapsulation part on the outer surface of the solid-state battery core, wherein the encapsulation part is a fiber prepreg subjected to heat treatment, and the temperature of the heat treatment is 60-300 ℃; at least one interface between the solid electrolyte membrane and the electrode plate is provided with an interface modification layer formed by thermal initiation; the temperature of the thermal initiation is 40-250 ℃. The interface modification layer is obtained by a thermal initiation in-situ polymerization or thermal initiation plasticization method, so that the structural battery has a good electrode/electrolyte interface and good cycle performance and rate performance; the fiber prepreg packaging part ensures that the structural battery has high bearing capacity; the interface modification layer and the fiber prepreg packaging part are selected according to the matching of the thermal initiation temperature and the thermal treatment temperature, and the respective functions are realized through synchronous heating, so that the battery performance is improved, and meanwhile, the manufacturing flow of the battery is greatly shortened.

Description

Structure battery based on solid-state battery cell, structure battery pack comprising structure battery cell and manufacturing method of structure battery pack
Technical Field
The invention relates to the technical field of chemical power supplies, in particular to a structural battery based on a solid-state battery core, a structural battery pack containing the same and a manufacturing method of the structural battery pack.
Background
Commercial lithium ion batteries use transition metal oxides or polyanion metal oxides as positive electrode active materials, graphite as negative electrode active materials, and ester electrolyte or polymer gel as electrolyte. However, the conventional liquid electrolyte has poor high temperature resistance, which tends to cause serious safety problems. The solid-state battery using the solid-state electrolyte to replace the organic electrolyte has the advantages of high energy density, high safety and the like, and provides a promising solution for the next-generation energy storage device. At present, the performance of a solid-state battery cell is mainly influenced by the ion transmission speed of an electrode-solid electrolyte solid interface.
The traditional battery energy storage system has the disadvantages of large volume, large weight, poor corrosion resistance, easy damage and relatively short service life, and is greatly limited in application in industry. In recent years, a structural battery integrating a load bearing structure and an energy storage function has been developed. The structural battery simultaneously provides higher requirements on the mechanical strength and the electrochemical performance of the whole battery.
The invention patent with publication number of CN 111600056B discloses a preparation method of an energy storage composite structure battery, which comprises the following steps: placing electrode plates on two sides of a diaphragm to perform Z-type lamination to prepare a battery cell; preparing a shell by using prepreg and foam materials, and then forming a sandwich structure by placing the battery cell in the shell; hot-pressing and compounding to form through a molding press; injecting an electrolytic liquid; sealing and testing. Although the scheme discloses that the obtained structural battery has better mechanical impact resistance, a liquid injection hole is reserved in the preparation process, and the liquid injection hole is sealed by an explosion-proof plug after liquid injection. The filling hole may still be a weak point of impact resistance of the battery, and the battery cannot overcome the defects of the battery based on the liquid electrolyte.
The invention patent with publication number CN 113036268A discloses a lithium metal structure battery which is composed of a structure cathode, a structure electrolyte, a lithium metal anode, a tab and a fiber/epoxy composite material packaging material. The lithium metal anode adopts protective treatment measures. The structural electrolyte is composed of an inorganic electrolyte and a polymer electrolyte reinforced by glass fibers together. The structural battery adopts the carbon fiber reinforced structural cathode and anode to greatly improve the mechanical strength index, and adopts lithium metal as the anode to improve the electrochemical performance of the structural battery. However, on the one hand, the structured customization of the components in this solution increases the manufacturing difficulty, and on the other hand, this solution does not take into account the optimization of the interfacial properties of the electrodes and the electrolyte within the structured cell.
Therefore, developing a solid-state cell-based structural battery that is easy to manufacture and has optimized interface performance is a technical problem that needs to be solved.
Disclosure of Invention
Because of the defects in the prior art, the invention provides a structure battery based on a solid-state battery core, a structure battery pack containing the structure battery pack and a manufacturing method thereof, so as to solve the problems of limited ion transmission of a solid-state battery core electrode-solid electrolyte solid interface and complex manufacturing process of the structure battery.
In order to achieve the above object, in a first aspect, the present invention provides a structural battery based on a solid-state battery cell, where the solid-state battery cell includes a positive electrode plate, a negative electrode plate, and a solid electrolyte membrane, the positive electrode plate and the negative electrode plate are alternately stacked, and the solid electrolyte membrane is alternately arranged between the adjacent positive electrode plate and negative electrode plate, and is characterized in that: the structure battery comprises the solid-state battery core and an encapsulation part on the outer surface of the solid-state battery core, wherein the encapsulation part is fiber prepreg subjected to heat treatment, and the temperature of the heat treatment of the fiber prepreg is 60-300 ℃; at least one interface between the solid electrolyte membrane and the positive plate and at least one interface between the solid electrolyte membrane and the negative plate are provided with interface modification layers formed by thermal initiation; the temperature of the thermal initiation is 40-250 ℃; the interface modification layer is in good contact with the solid electrolyte membrane and the electrode plates at the two sides; the heat stability temperature of the positive plate, the negative plate and the solid electrolyte membrane is higher than the heat treatment temperature of the fiber prepreg and the heat initiation temperature of the interface modification layer.
Preferably, the solid electrolyte membrane is a flexible polymer solid electrolyte membrane or an organic-inorganic composite solid electrolyte membrane; the positive electrode plate, the negative electrode plate and the solid electrolyte membrane in the solid battery cell are arranged in a laminated or winding mode.
Preferably, the solid electrolyte membrane is a polymer solid electrolyte membrane, an inorganic solid electrolyte membrane, or an organic-inorganic composite solid electrolyte membrane; the positive electrode plate, the negative electrode plate and the solid electrolyte membrane in the solid battery cell are arranged in a laminated mode.
Preferably, the fiber prepreg is any one of carbon fiber prepreg, glass fiber prepreg, aramid fiber prepreg and hybrid fiber prepreg; and/or the active material of the positive plate is any one or at least two of lithium iron phosphate, lithium cobalt oxide, lithium manganate, lithium nickel manganate, lithium vanadium phosphate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate and lithium manganate; and/or the active material of the negative plate is any one or at least two of lithium metal, graphite, lithium titanate, niobium titanium oxide, silicon and silicon-carbon composite materials.
In a second aspect, the present invention provides a method for manufacturing the structural battery, comprising the steps of:
step S11, mixing a polymer monomer, an initiator for polymerization of the polymer monomer, lithium salt and an electrolyte solvent to obtain a liquid interface modification precursor;
step S12, brushing the interface modification precursor on the surfaces of the positive plate and/or the negative plate, and sequentially laminating the positive plate, the solid electrolyte membrane, the negative plate and the solid electrolyte membrane, and then laminating or winding the laminated positive plate, the solid electrolyte membrane and the solid electrolyte membrane to obtain the solid battery cell;
s13, packaging the solid-state battery cells by adopting fiber prepreg;
step S14, heating and curing the packaging body obtained in the step S13 to obtain the structural battery; and the interface modification precursor is subjected to thermal initiation polymerization to form an interface modification layer, and the fiber prepreg is subjected to thermal treatment, solidification and molding to synchronously finish the process.
Preferably, the polymer monomer comprises any one or at least two of 1, 3-dioxolane monomer, acrylic ester monomer (methyl acrylate, ethyl acrylate, propyl acrylate and the like), allyl methyl carbonate, vinyl acetate and vinylene carbonate; and/or the initiator comprises any one or a combination of at least two of azodiisobutyronitrile, dibenzoyl peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate and 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide.
In a third aspect, the present invention provides a method for manufacturing the structural battery, which is characterized by comprising the following steps:
step S21, covering a layer of thermoplastic polymer electrolyte film on the surface of the positive plate and/or the negative plate, sequentially stacking the positive plate, the solid electrolyte membrane, the negative plate and the solid electrolyte membrane, and then laminating or winding to obtain the solid battery cell;
s22, packaging the solid-state battery cells by adopting fiber prepreg;
step S23, heating and curing the packaging body obtained in the step S22 to obtain the structural battery; the thermoplastic polymer electrolyte film is subjected to thermal initiation to form an interface modification layer, and the fiber prepreg is subjected to thermal treatment, solidification and molding to synchronously finish the process.
Preferably, the thermoplastic polymer electrolyte film includes any one or at least two of polyethylene oxide containing lithium salt, polypropylene oxide, polyvinylidene fluoride, polyacrylonitrile resin, polyacrylate polymer (such as polymethyl methacrylate, etc.), carbonate polymer. Acrylic polymers such as polymethyl methacrylate, and carbonate polymers such as polyethylene carbonate, polytrimethylene carbonate and polytrimethylene carbonate.
In a fourth aspect, the present invention provides a structural battery produced by the above-described production method.
In a fifth aspect, the present invention provides a structural battery pack comprising the structural battery described above or the structural battery manufactured by the manufacturing method described above; preferably, the structural battery pack is of a honeycomb structure, and the structural battery is embedded in the honeycomb core and is fixed by upper and lower layers of panels and structural adhesive.
In a final aspect, the present invention provides an electric device, wherein the electric device is provided with the structural battery, the structural battery manufactured by the manufacturing method, or the structural battery pack.
Compared with the prior art, the invention has the following advantages or beneficial effects:
(1) The interface modification layer of the solid-state battery core is obtained by a thermal initiation in-situ polymerization or thermal initiation plasticization method, so that the structural battery has a good electrode/electrolyte interface and good cycle performance and rate performance; the fiber prepreg packaging part ensures that the structural battery has high bearing capacity;
(2) According to the invention, the interface modification layer and the fiber prepreg packaging part are selected according to the matching of the thermal initiation temperature and the thermal treatment temperature, and the respective functions are realized through synchronous heating, so that the battery performance is improved, and meanwhile, the manufacturing flow of the battery is greatly shortened;
(3) The invention is applicable to various organic, inorganic or composite solid electrolyte membranes and various anode and cathode materials, and has the advantages of easily available raw materials and wide application range;
(4) The manufacturing method is suitable for large-scale production, and the manufacturing cost of the product is low.
Drawings
The invention and its features and advantages will become more apparent from reading of the detailed description of non-limiting embodiments, given with reference to the following drawings. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention.
Fig. 1 is a schematic cross-sectional view of a structural battery according to an embodiment of the present invention;
FIG. 2 is a graph showing an impact resistance test of a structural battery according to an embodiment of the present invention;
FIG. 3 is an optical image of a structural battery 25J according to an embodiment of the present invention after impact testing;
FIG. 4 is a tensile test curve of a structural battery according to an embodiment of the present invention;
FIG. 5 is an AC impedance spectrum of a structural battery according to an embodiment of the present invention;
FIG. 6 is a graph of battery cycling performance at a current density of 0.1C for a structural battery according to an embodiment of the present invention;
FIG. 7 is a graph showing the first charge and discharge curves of a structural battery according to an embodiment of the present invention after impact loading;
fig. 8 is an ac impedance spectrum of the structural battery of comparative example 1 of the present invention;
FIG. 9 is a graph showing the cycle performance of the structural battery of comparative example 1 of the present invention at a current density of 0.1C;
in the figure, 1, a positive plate; 2. a negative electrode sheet; 3. a solid electrolyte membrane; 4. a fibrous prepreg; 5. and an interface modification layer.
Detailed Description
The technical solutions in the embodiments will be clearly and completely described below with reference to the drawings in the examples of the present invention. It will be apparent that the embodiments described below are only some, but not all, embodiments of the invention.
The terms "comprises," "comprising," and any variations thereof, in the following embodiments and examples, are intended to cover a non-exclusive inclusion, such that a process, method, article, or article that comprises a list of steps or elements is not limited to only those steps or elements but may, optionally, include other steps or elements not listed or inherent to such process, method, article, or article.
In the following examples and examples, raw materials such as a device, a monomer compound, an initiator, and an organic solvent are commercially available, and a detection instrument and a detection reagent are commercially available, and the detection method used is a retrievable prior art. For example, drop hammer impact performance was tested using an Amsler HIT1100F (maximum impact energy: 100J; punch diameter: 15 mm) apparatus according to ASTM D7136/D7136M-12; tensile properties were tested according to ASTM D3039/D3039M-07 using a Zwick Roell GmbH & Co.KG,250kN apparatus.
Example 1
Referring to fig. 1, the embodiment provides a solid-state cell based structural battery, the solid-state cell includes a positive plate 1, a negative plate 2 and a solid electrolyte membrane 3, the positive plate 1 and the negative plate 2 are alternately stacked, the solid electrolyte membrane 3 is alternately arranged between the adjacent positive plate 1 and negative plate 2 in a penetrating manner, the structural battery includes a solid-state cell and an encapsulation part on the outer surface of the solid-state cell, the encapsulation part is a fiber prepreg 4 subjected to heat treatment, and the heat treatment temperature of the fiber prepreg 4 is 60-300 ℃; at least one interface between the solid electrolyte membrane 3 and the positive electrode plate 1 and at least one interface between the solid electrolyte membrane 3 and the negative electrode plate 2 is provided with an interface modification layer 5 formed by thermal initiation; the temperature of the thermal initiation is 40-250 ℃; the interface modification layer 5 is well contacted with the solid electrolyte membrane 3 and the electrode plates at the two sides; the heat stabilization temperature of the positive electrode sheet 1, the negative electrode sheet 2 and the solid electrolyte membrane 3 is higher than the temperature of the heat treatment of the fiber prepreg 4 and the temperature of the heat initiation of the interface modification layer 5.
As a preferred embodiment, the interface modification layer 5 comprises a polymer component having ionic conductivity thermally induced to form at the interface. As an example, the interface modification layer between the positive electrode sheet 1 and the solid electrolyte membrane 3 is a layer of lithium salt-containing acrylate-based polymer electrolyte polymerized in situ at the interface.
As a preferred technical scheme, further: the solid electrolyte membrane 3 is a flexible polymer solid electrolyte membrane or an organic-inorganic composite solid electrolyte membrane; the positive plate 1, the negative plate 2 and the solid electrolyte membrane 3 in the solid battery core are arranged in a laminated or winding mode. As an alternative technical scheme: the solid electrolyte membrane 3 is a polymer solid electrolyte membrane, an inorganic solid electrolyte membrane, or an organic-inorganic composite solid electrolyte membrane; the positive plate 1, the negative plate 2 and the solid electrolyte membrane 3 in the solid battery cell are arranged in a laminated mode. The polymer solid electrolyte membrane can be any one or a combination of at least two of polyethylene oxide, poly 1, 3-dioxolane, polyallylmethyl carbonate, polyvinyl acetate, polyethylene carbonate and polyacrylate as a matrix electrolyte membrane. The inorganic solid electrolyte membrane may be an oxide or sulfide, and the oxide may be a NASICON-type oxide lithium ion conductor such as Li 1.5 Al 0.5 Ge 1.5 P 3 O 12 (LAGP)、Li 1.3 Al 0.3 Ti 1.7 P 3 O 12 (LATP); the sulfide may be a binary sulfide or a ternary sulfide, such as Li 2 S-P 2 S 5 、Li 2 S-MeS 2 -P 2 S 5 Where me= Si, ge, sn, al, etc. The organic-inorganic composite solid electrolyte membrane may be a composite formed of a polymer matrix and lithium salt, inorganic solid electrolyte powder, or fibers.
As a preferred technical scheme, further: the fiber prepreg 4 is any one of carbon fiber prepreg, glass fiber prepreg, aramid fiber prepreg and hybrid fiber prepreg; and/or the active material of the positive plate 1 is any one or at least two of lithium iron phosphate, lithium cobalt oxide, lithium manganate, lithium nickel manganate, lithium vanadium phosphate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate and lithium rich manganate; and/or the active material of the negative electrode sheet 2 is any one or at least two of lithium metal, graphite, lithium titanate, niobium titanium oxide, silicon and silicon-carbon composite materials.
As a preferred technical scheme, further: the temperature of the heat initiation is not higher than the temperature of the heat treatment. For example, the interface modifying layer has a thermal initiation temperature of 70 to 90 ℃; the heat treatment temperature of the fiber prepreg is 100-130 ℃. This feature ensures that the interface modifying layer completes curing before the fiber prepreg in the heat treatment process, and can better ensure the vacuum degree inside the structural battery.
The manufacturing method of the battery with the structure comprises the following steps:
step S11, mixing a polymer monomer, an initiator for polymerization of the polymer monomer, lithium salt and an electrolyte solvent to obtain a liquid interface modification precursor;
step S12, brushing the interface modification precursor on the surfaces of the positive plate and/or the negative plate, and sequentially laminating the positive plate, the solid electrolyte membrane, the negative plate and the solid electrolyte membrane, and then laminating or winding the laminated positive plate, the solid electrolyte membrane and the solid electrolyte membrane to obtain the solid battery cell; the liquid interface modification precursor can fill gaps between the electrode material and the solid electrolyte membrane, and simultaneously infiltrate into the electrode material to form good contact with the solid electrolyte membrane 3 and the electrode plates at two sides;
s13, packaging the solid-state battery cells by adopting fiber prepreg;
step S14, heating and curing the packaging body obtained in the step S13 to obtain the structural battery; and the interface modification precursor is subjected to thermal initiation polymerization to form an interface modification layer, and the fiber prepreg is subjected to thermal treatment, solidification and molding to synchronously finish the process.
As a preferred technical scheme, further:
the curing and molding method in step S14 may be autoclave molding, resin transfer molding, vacuum bag molding, winding molding, etc.
As a preferred technical scheme, further:
the polymer monomer comprises any one or at least two of 1, 3-dioxolane monomer, acrylic ester monomer (methyl acrylate, ethyl acrylate, propyl acrylate and the like), allyl methyl carbonate, vinyl acetate and vinylene carbonate; and/or the initiator comprises any one or a combination of at least two of azodiisobutyronitrile, dibenzoyl peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate and 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide.
As a preferred technical scheme, further:
the precursor of the solid electrolyte membrane is the same as or similar to the precursor of the interface modification layer, and the solid electrolyte membrane is synthesized for standby by thermally initiated polymerization before the step S11. The feature enables the interface modification layer to have good interface compatibility with the solid electrolyte membrane; the precursor of the solid electrolyte membrane can be used as the precursor of the interface modification layer or the base solution thereof at the same time, so that the manufacturing cost is reduced; the liquid interface modification precursor can fill the gap between the electrode material and the solid electrolyte membrane and penetrate into the electrode material to provide ionic conductance.
As a preferred technical scheme, further:
the solid electrolyte membrane comprises an acrylic polymer, an initiator, lithium salt and carbonate organic compounds; based on the total weight of the solid electrolyte, the content of the acrylic polymer is 30-60%; the content of the initiator is 0.5-1.5%; the content of the lithium salt is 5-20%; the content of the carbonic ester organic compound is 30-70%; the acrylic polymer is formed by initiating polymerization of two or more acrylic polymer monomers through an initiator.
Further: the acrylate-based polymer monomer comprises at least one acrylic ester monomer A with a chain structure and at least one acrylic ester monomer B with a benzene ring structure; based on the total weight of the acrylic polymer, the content of the acrylic polymer monomer A is 30-50%; the content of the acrylic polymer monomer B is 50-70%.
The inventors of the present invention found that the relative content of acrylate monomer a containing a compliant alkyl chain and acrylate monomer B containing a rigid benzene ring structure is critical; the solid electrolyte with mechanical properties suitable for lamination and winding is obtained only at a suitable relative content.
The initiator comprises any one or a combination of at least two of azodiisobutyronitrile, dibenzoyl peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate and 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide; the lithium salt includes lithium hexafluorophosphate (LiPF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium dioxalate borate (LiBOB), lithium perchlorate (LiClO) 4 ) Lithium difluorooxalato borate (LiDFOB), lithium triflate (LiCF) 3 SO 3 ) Lithium bis (trifluoromethane sulfonate) (LiN (SO) 2 CF 3 ) 2 ) Any one or a combination of at least two of the following; the carbonate-based organic compound includes any one or a combination of at least two of diethyl carbonate (DEC), ethylmethyl carbonate (EMC), dimethyl carbonate (DMC), propylene Carbonate (PC) and Ethylene Carbonate (EC).
In addition, the carbonate organic compound can also comprise any one or at least two additives of fluoroethylene carbonate, fluoromethyl ethylene carbonate and methyl trifluoroethyl carbonate, so as to further improve the stability of the polymer electrolyte under the conditions of high pressure, low temperature and the like.
The structural formula of the compound of the chemical components can show that the solid electrolyte for the battery cell uses the polyacrylate frame as a structural phase and the carbonate electrolyte as an ion-conducting phase, and the prepared solid polymer electrolyte membrane has high flexibility and high ion conductivity and can realize the winding assembly of the solid battery cell. The invention adopts the chain acrylic ester monomer A and the acrylic ester monomer B with benzene ring structure as precursors to manufacture the crosslinked product, so that the chain structure of the crosslinked product has a flexible alkyl chain and a rigid benzene ring phase connection structure, and the polymer electrolyte has high rigidity and good toughness. Meanwhile, the introduction of the liquid phase of the carbonate organic compound in the crosslinked network provides a rapid lithium ion transmission channel for lithium ions, and improves the ion conductivity of the lithium ions.
In order to further assist in understanding the technical solution of the present embodiment, the technical solution of the present embodiment is described in more detail by the following examples.
EXAMPLE 1,
Step S11.1, preparing a solid electrolyte membrane, preparing electrode slurry, and respectively preparing a positive plate and a negative plate: the solid electrolyte membrane comprises an acrylic polymer, an initiator, lithium salt and carbonate organic compounds; the content of the acrylic polymer is 49.5 percent based on the total weight of the solid electrolyte; the content of the initiator is 0.5%; the content of the lithium salt is 20%; the content of the acid ester organic compound is 30%. The acrylic polymer is prepared by initiating polymerization of an isopentyl tetraacrylate monomer and bisphenol A ethoxylated dimethacrylate by taking azobisisobutyronitrile as an initiator. The mass ratio of the isopentyl tetraacrylate monomer to the bisphenol A ethoxylated dimethacrylate is 1:2. lithium perchlorate is used as lithium salt, and diethyl carbonate and ethylmethyl carbonate are used as carbonate organic compounds. Specifically, the preparation process of the solid electrolyte membrane is as follows:
first, an electrolyte precursor is prepared: mixing the isopentyl tetraacrylate monomer, bisphenol A ethoxylated dimethacrylate, azodiisobutyronitrile, lithium perchlorate, diethyl carbonate and methyl ethyl carbonate according to the formula, and fully stirring to uniformly mix the monomers;
secondly, curing and film forming: the electrolyte precursor in liquid state is sandwiched between glass plates, and a spacer of 25 μm is placed, and then the electrolyte precursor is placed in a curing oven to heat to initiate curing reaction until curing is complete, thus obtaining a solid electrolyte membrane of 20 μm.
From the above manufacturing process, it can be seen that the solid electrolyte membrane is manufactured by a method of thermally initiating monomer polymerization and liquid phase separation, and the manufacturing method is simple and low in cost.
Preparation of electrode slurry: mixing graphite, conductive carbon black Super P and polyvinylidene fluoride (PVDF) binder according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone (NMP) solvent, and uniformly stirring to obtain uniformly mixed sticky slurry for preparing a negative electrode; lithium iron phosphate (LiFePO) 4 ) And (3) proportioning conductive carbon black Super P and PVDF binder according to the mass ratio of 8:1:1, adding a proper amount of NMP solvent, and uniformly stirring to obtain uniformly mixed sticky slurry for preparing the anode.
Preparing positive and negative plates: respectively coating the uniformly mixed positive/negative electrode slurry on an aluminum/copper current collector; in this example, aluminum foil having a thickness of 10 μm and copper foil having a thickness of 10 μm were used as current collectors, and electrode paste was coated on the aluminum foil to a thickness of 30 μm. And (3) putting the coated electrode slices into a vacuum drying oven at 120 ℃ for drying for 12 hours, and then cutting the electrode slices into the electrode slices with proper shapes.
And step S12.1, uniformly brushing the electrolyte precursor serving as an interface modification layer precursor on the positive plate and the negative plate, and respectively placing the electrolyte precursor on two sides of the solid electrolyte membrane for winding.
And S13.1, sealing the outer side of the winding solid-state battery cell by adopting carbon fiber prepreg cloth.
S14.1, winding the solid-state battery core with the carbon fiber prepreg cloth sealed, and placing the solid-state battery core in a curing oven for curing and forming by a vacuum bag; firstly, raising the temperature to 80 ℃, and preserving the heat for 40min; and vacuumizing, raising the temperature to 120 ℃, preserving heat for 90min, closing the curing oven, and taking out the battery after the battery is naturally cooled to obtain the structural battery. The interface modification precursor is heated to 90 ℃ to form an interface modification layer through thermal initiation polymerization, the fiber prepreg is cured and molded when heated to 120 ℃, and the packaging body is cured at 120 ℃.
Referring to fig. 2, the structural battery obtained in this example was subjected to an impact resistance test of 25J. Fig. 3 shows an optical image of the structural cell after 25J impact testing. As can be seen from the photo, the external structure of the structural battery is complete and has no cracks, and the structural battery has good impact resistance. Fig. 4 shows a tensile property test curve of the structural battery. The structural battery has the advantages that under the stress of 0-250 MPa, the strain changes linearly, the strain is only about 1%, and the elastic modulus is 25GPa. Moreover, the structural battery can still be charged and discharged normally after the tensile property test. Referring to fig. 5, the interfacial resistance of the structural battery was 650 Ω, and the interfacial resistance remained substantially stable over 500 cycles. This benefits from the improvement in interfacial properties of the interfacial modification layer between the electrode sheet and the electrolyte. Fig. 6 shows the cycle curve of the structural battery at a current density of 0.1C. The capacity retention of the wound solid state cell in 200 cycles was 90%. Fig. 7 shows the first-turn charge-discharge curve of the structural battery after impact load (25J) is applied. After being impacted, the first-turn capacity of the structural battery is as high as 1.62mAh.
Example 2
The embodiment provides a manufacturing method of a structural battery and the structural battery manufactured by the method. The manufacturing method comprises the following steps:
step S21, covering a layer of thermoplastic polymer electrolyte film on the surface of the positive plate and/or the negative plate, sequentially stacking the positive plate, the solid electrolyte membrane, the negative plate and the solid electrolyte membrane, and then laminating or winding to obtain the solid battery cell;
s22, packaging the solid-state battery cells by adopting fiber prepreg;
step S23, heating and curing the packaging body obtained in the step S22 to obtain the structural battery; the thermoplastic polymer electrolyte film is subjected to thermal initiation to form an interface modification layer, and the fiber prepreg is subjected to thermal treatment, solidification and molding to synchronously finish the process.
As a preferred technical scheme, further: the thermoplastic polymer electrolyte film comprises any one or at least two of polyethylene oxide containing lithium salt, polypropylene oxide, polyvinylidene fluoride, polyacrylonitrile resin, acrylic polymers and carbonic acid ester polymers. Acrylic polymers such as polymethyl methacrylate, and carbonate polymers such as polyethylene carbonate, polytrimethylene carbonate and polytrimethylene carbonate.
The structure of the solid-state battery cell based on the solid-state battery cell manufactured by the method is similar to that of the embodiment 1, the solid-state battery cell based on the solid-state battery cell comprises a positive plate, a negative plate and a solid electrolyte membrane, wherein the positive plate and the negative plate are arranged in a staggered and laminated mode, the solid electrolyte membrane is arranged between the adjacent positive plate and negative plate in a staggered and penetrating mode, the solid-state battery cell comprises the solid-state battery cell and a packaging part on the outer surface of the solid-state battery cell, and the packaging part is fiber prepreg subjected to heat treatment; at least one interface between the solid electrolyte membrane 3 and the positive plate 1 and at least one interface between the solid electrolyte membrane and the negative plate are provided with interface modification layers formed by thermal initiation; the interface modification layer is well contacted with the solid electrolyte membranes and the electrode plates at the two sides and provides ionic conductivity; the heat stability temperature of the positive plate, the negative plate and the solid electrolyte membrane is higher than the heat treatment temperature of the fiber prepreg and the heat initiation temperature of the interface modification layer. The interface modifying layer includes a thermally induced polymer component and an active component of an electrode sheet adjacent thereto. Unlike example 1, as an example, a thermoplastic polymer electrolyte thin film between a positive electrode sheet and a solid electrolyte membrane is softened by heating at the surface of a positive electrode active material and is composited with the positive electrode active material to form an interface modification layer.
The thermoplastic polymer electrolyte film is softened in the heat treatment process of the battery, fills gaps between the electrode material and the solid electrolyte membrane, and permeates the electrode material, so that the solid battery core of the structural battery has a better electrode/electrolyte interface.
In order to further assist in understanding the technical solution of the present embodiment, the technical solution of the present embodiment is described in more detail by the following examples.
EXAMPLE 2,
Step S21.1, preparing a solid electrolyte membrane, preparing electrode slurry, and respectively preparing a positive plate and a negative plate:
(1) Manufacturing electrode slurry: mixing lithium titanate, conductive carbon black Super P and polyvinylidene fluoride (PVDF) binder according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone (NMP) solvent, and uniformly stirring to obtain uniformly mixed sticky slurry for manufacturing a negative electrode; mixing lithium manganate, conductive carbon black Super P and PVDF binder according to the mass ratio of 8:1:1, adding a proper amount of NMP solvent, and uniformly stirring to obtain a uniformly mixed sticky slurry for manufacturing the anode.
(2) Coating: respectively coating the uniformly mixed positive/negative electrode slurry on an aluminum/copper current collector; in this example, aluminum foil having a thickness of 20 μm and copper foil having a thickness of 20 μm were used as current collectors, and the electrode paste was coated on the aluminum foil to a thickness of 50 μm.
(3) Drying and slicing: and (3) putting the coated electrode slices into a vacuum drying oven at 120 ℃ for drying for 12 hours, and then cutting the electrode slices into the electrode slices with proper shapes.
Next, a 43 μm thick solid electrolyte membrane was produced using a 50 μm thick mold by the method for producing a solid electrolyte for a cell in example 1.
And S21.2, covering a layer of polyethylene oxide electrolyte film containing lithium bis (trifluoromethanesulfonyl) imide on the upper surfaces of the positive plate and the negative plate, and respectively placing the polyethylene oxide electrolyte film on two sides of the solid electrolyte for winding.
And S22.1, sealing the outer side of the wound solid-state battery cell by adopting glass fiber prepreg cloth.
S23.1, winding the solid-state battery core with the glass fiber prepreg cloth sealed, and placing the solid-state battery core in a curing oven for autoclave curing molding; firstly, raising the temperature to 200 ℃, and preserving the heat for 40min; and then the temperature is increased to 240 ℃, the temperature is kept for 90 minutes, the curing oven is closed, and the structural battery is obtained after the curing oven is naturally cooled. The interface modification precursor is softened by heat initiation when heated to 200 ℃ to form an interface modification layer, and the fiber prepreg is cured and molded when heated to 240 ℃.
Comparative example
The structural battery provided in this comparative example was similar to the structure and the manufacturing method in example 1, except that the structural battery in this comparative example did not include an interface modification layer, and the production process did not involve the generation of an interface modification layer. Referring to fig. 8, the interface resistance of the structural battery is 4000 Ω. Compared with the interface modification layer between the electrode plate and the electrolyte, the interface resistance is obviously increased, and the improvement effect of the interface modification layer on the interface performance is further verified. Fig. 9 shows a cycle curve of the structural battery at a current density of 0.1C, and the high interface resistance significantly deteriorates the charge and discharge performance.
The performance data in comparative example 1 and comparative example show that the structural battery of example 1 has a smaller cell interface resistance and better cycle performance, which benefits from the interface modification layer enhancing ion and electron transport at the electrode and electrolyte interface, thereby reducing the internal resistance of the battery and enhancing the stability of the electrochemical interface and charge-discharge performance.
Example 3
The present embodiment provides a structural battery pack including the structural battery in embodiment 1 or embodiment 2; preferably, the structural battery pack is of a honeycomb structure, and the structural battery is embedded in the honeycomb core and is fixed by upper and lower layers of panels and structural adhesive.
As an example, a specific preparation method of the honeycomb-structured battery pack is as follows:
(1) Horizontally placing the panel, and paving a layer of structural adhesive;
(2) Placing the honeycomb core on the structural adhesive;
(3) Embedding the structural battery in the embodiment 1 or the embodiment 2 into the honeycomb core, and covering the structural adhesive and the other side panel;
(4) And (5) solidifying and forming the structural adhesive to obtain the honeycomb structure battery pack.
As a preferred technical scheme, further: the honeycomb core of the honeycomb structure battery comprises aluminum honeycomb, aramid paper honeycomb, stainless steel honeycomb, glass cloth honeycomb and the like; the panel comprises a stainless steel plate, an aluminum plate, a galvanized plate and the like.
Example 4
The present embodiment provides an electric device on which the structural battery described in embodiment 1 or 2 or the structural battery pack described in embodiment 3 is mounted. The electric equipment may be any equipment, such as a vehicle, an unmanned aerial vehicle, or the like, on which the structural battery described in embodiment 1 or 2 or the structural battery pack described in embodiment 3 can be mounted.
In summary, the invention discloses a structural battery based on a solid-state cell, a structural battery pack containing the same and a manufacturing method thereof. The structural battery comprises the solid-state battery core and an encapsulation part on the outer surface of the solid-state battery core, wherein the encapsulation part is a fiber prepreg subjected to heat treatment, and the temperature of the heat treatment is 60-300 ℃; at least one interface between the solid electrolyte membrane and the electrode plate is provided with an interface modification layer formed by thermal initiation; the temperature of the thermal initiation is 40-250 ℃. The interface modification layer is obtained by a thermal initiation in-situ polymerization or thermal initiation plasticization method, so that the structural battery has a good electrode/electrolyte interface and good cycle performance and rate performance; the fiber prepreg packaging part ensures that the structural battery has high bearing capacity; the interface modification layer and the fiber prepreg packaging part are selected according to the matching of the thermal initiation temperature and the thermal treatment temperature, and the respective functions are realized through synchronous heating, so that the battery performance is improved, and meanwhile, the manufacturing flow of the battery is greatly shortened.
The order of execution of the operations, steps, and the like in the apparatus and methods shown in the claims, the specification, and the drawings may be performed in any order as long as the order is not particularly specified, and as long as the output of the preceding process is not used in the following process. The use of the description of "first," "second," "again," etc. for convenience of description does not imply that the implementations must be performed in such order.
Those skilled in the art will understand that the skilled person can implement the modification in combination with the prior art and the above embodiments, and this will not be repeated here. Such modifications do not affect the essence of the present invention, and are not described herein.
The preferred embodiments of the present invention have been described above. It is to be understood that the invention is not limited to the specific embodiments described above, wherein devices and structures not described in detail are to be understood as being implemented in a manner common in the art; any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or modifications to equivalent embodiments without departing from the scope of the technical solution of the present invention, using the methods and technical contents disclosed above, without affecting the essential content of the present invention. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.

Claims (11)

1. The utility model provides a structure battery based on solid-state electric core, solid-state electric core includes positive plate, negative plate and solid electrolyte membrane, and positive plate and negative plate are crisscross to be stacked and set up, solid electrolyte membrane is crisscross to be worn to locate adjacent between positive plate with the negative plate, its characterized in that:
the structure battery comprises the solid-state battery core and an encapsulation part on the outer surface of the solid-state battery core, wherein the encapsulation part is fiber prepreg subjected to heat treatment, and the temperature of the heat treatment of the fiber prepreg is 60-300 ℃; at least one interface between the solid electrolyte membrane and the positive plate and at least one interface between the solid electrolyte membrane and the negative plate are provided with interface modification layers formed by thermal initiation; the temperature of the thermal initiation is 40-250 ℃; the interface modification layer is in good contact with the solid electrolyte membrane and the electrode plates at the two sides; the heat stability temperature of the positive plate, the negative plate and the solid electrolyte membrane is higher than the heat treatment temperature of the fiber prepreg and the heat initiation temperature of the interface modification layer.
2. The solid state cell based structural battery of claim 1, wherein the solid state electrolyte membrane is a flexible polymer solid state electrolyte membrane or an organic-inorganic composite solid state electrolyte membrane; the positive electrode plate, the negative electrode plate and the solid electrolyte membrane in the solid battery cell are arranged in a laminated or winding mode.
3. The solid state cell based structural battery according to claim 1, wherein the solid electrolyte membrane is a polymer solid electrolyte membrane, an inorganic solid electrolyte membrane, or an organic-inorganic composite solid electrolyte membrane; the positive electrode plate, the negative electrode plate and the solid electrolyte membrane in the solid battery cell are arranged in a laminated mode.
4. The solid state cell based structural battery of claim 1, 2 or 3, wherein the fiber prepreg is any one of carbon fiber prepreg, glass fiber prepreg, aramid fiber prepreg, hybrid fiber prepreg; and/or the active material of the positive plate is any one or at least two of lithium iron phosphate, lithium cobalt oxide, lithium manganate, lithium nickel manganate, lithium vanadium phosphate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate and lithium manganate; and/or the active material of the negative plate is any one or at least two of lithium metal, graphite, lithium titanate, niobium titanium oxide, silicon and silicon-carbon composite materials.
5. A method of manufacturing the structural battery according to any one of claims 1 to 4, comprising the steps of:
step S11, mixing a polymer monomer, an initiator for polymerization of the polymer monomer, lithium salt and an electrolyte solvent to obtain a liquid interface modification precursor;
step S12, brushing the interface modification precursor on the surfaces of the positive plate and/or the negative plate, and sequentially laminating the positive plate, the solid electrolyte membrane, the negative plate and the solid electrolyte membrane, and then laminating or winding the laminated positive plate, the solid electrolyte membrane and the solid electrolyte membrane to obtain the solid battery cell;
s13, packaging the solid-state battery cells by adopting fiber prepreg;
step S14, heating and curing the packaging body obtained in the step S13 to obtain the structural battery; and the interface modification precursor is subjected to thermal initiation polymerization to form an interface modification layer, and the fiber prepreg is subjected to thermal treatment, solidification and molding to synchronously finish the process.
6. The method according to claim 5, wherein the polymer monomer comprises one or more of 1, 3-dioxolane monomer, acrylic monomer (methyl acrylate, ethyl acrylate, propyl acrylate, etc.), allyl methyl carbonate, vinyl acetate, and vinylene carbonate; and/or the initiator comprises any one or a combination of at least two of azodiisobutyronitrile, dibenzoyl peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate and 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide.
7. A method of manufacturing the structural battery according to any one of claims 1 to 4, comprising the steps of:
step S21, covering a layer of thermoplastic polymer electrolyte film on the surface of the positive plate and/or the negative plate, sequentially stacking the positive plate, the solid electrolyte membrane, the negative plate and the solid electrolyte membrane, and then laminating or winding to obtain the solid battery cell;
s22, packaging the solid-state battery cells by adopting fiber prepreg;
step S23, heating and curing the packaging body obtained in the step S22 to obtain the structural battery; the thermoplastic polymer electrolyte film is subjected to thermal initiation to form an interface modification layer, and the fiber prepreg is subjected to thermal treatment, solidification and molding to synchronously finish the process.
8. The method according to claim 7, wherein the thermoplastic polymer electrolyte film comprises any one or at least two of polyethylene oxide containing lithium salt, polypropylene oxide, polyvinylidene fluoride, polyacrylonitrile resin, an acrylic polymer, and a carbonate polymer.
9. A structural battery, characterized by being manufactured by the manufacturing method according to any one of claims 5 to 8.
10. A structural battery comprising two or more structural cells of any one of claims 1 to 4 or the structural cell of claim 9; preferably, the structural battery pack is of a honeycomb structure, and the structural battery is embedded in the honeycomb core and is fixed by upper and lower layers of panels and structural adhesive.
11. An electric device, characterized in that the structural battery according to any one of claims 1 to 4, the structural battery according to claim 9, or the structural battery pack according to claim 9 is mounted.
CN202310144346.8A 2023-02-21 2023-02-21 Structure battery based on solid-state battery cell, structure battery pack comprising structure battery cell and manufacturing method of structure battery pack Pending CN116154276A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116759639A (en) * 2023-08-17 2023-09-15 上海瑞浦青创新能源有限公司 Semi-solid battery and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116759639A (en) * 2023-08-17 2023-09-15 上海瑞浦青创新能源有限公司 Semi-solid battery and preparation method thereof
CN116759639B (en) * 2023-08-17 2023-11-28 上海瑞浦青创新能源有限公司 Semi-solid battery and preparation method thereof

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