CN111916777B - Light brine battery with lean solution structure - Google Patents
Light brine battery with lean solution structure Download PDFInfo
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- CN111916777B CN111916777B CN202010770982.8A CN202010770982A CN111916777B CN 111916777 B CN111916777 B CN 111916777B CN 202010770982 A CN202010770982 A CN 202010770982A CN 111916777 B CN111916777 B CN 111916777B
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
Abstract
The invention discloses a brine battery with a light-weight barren solution structure, which comprises an encapsulation film and a battery cell sealed in the encapsulation film; the battery cell is formed by overlapping and assembling an integrated electrode plate soaked with electrolyte and a diaphragm according to a Z shape, wherein the integrated electrode plate consists of a current collector matrix and electrode active substance layers loaded on the upper surface and the lower surface of the current collector matrix; the current collector substrate is a metal current collector substrate or a non-metal current collector substrate, and the thickness of the metal current collector substrate is 0.01-2.0 mm; the thickness of the nonmetal current collector substrate is 0.5-5.0 mm; the thickness of the electrode active material layer is 0-3 mm; the thickness of the diaphragm is 0.2-5 mm; a surfactant for reducing the surface tension of a solid-liquid interface is added to the electrolyte. The brine battery with the light-weight barren solution structure can effectively reduce the weight of the battery.
Description
Technical Field
The invention relates to a brine battery with a light-weight barren solution structure.
Background
The large-scale energy storage technology is the basis of new energy popularization and energy revolution, is an important component of national energy strategic demand layout, and plays an important role in national energy structure optimization and safe and stable operation of a power grid. The electrochemical energy storage battery has the advantages of high conversion efficiency, flexible assembly, no geographical environment constraint and the like, so that the electrochemical energy storage battery becomes a research hotspot of an energy storage technology, and the application of the electrochemical energy storage battery is gradually commercialized from demonstration. The large-scale energy storage technology faces the research and development application targets of low cost, long service life, high safety and easy recovery, and is particularly necessary for accelerating the breakthrough of the technical bottleneck and exploring a new technology. The development of lithium ion batteries based on organic electrolytes is quite mature, and the lithium ion batteries are widely applied to portable mobile electronic equipment, electric automobiles and various high specific energy application scenes. However, as a large-scale integrated energy storage application (a scale of more than 1 MWh), due to the influences of the consistency of single batteries, the difficulty of integrated control and the like, a series of safety (combustion) accidents of energy storage systems and power stations occur globally in recent years. Due to the characteristics of large investment, long operation and maintenance period and the like, the intrinsic safety of the battery is more and more emphasized, and the method is also a difficult problem which needs to be solved urgently in the scale popularization of the existing energy storage battery. Energy storage batteries using aqueous electrolytes generally have a high safety. Such as lead-acid batteries, which have been developed for 150 years, but have problems of environmental pollution, short life, and the like. In recent years, a saline energy storage battery based on an aqueous electrolyte (with neutral pH) attracts extensive attention of researchers, and one main characteristic of the technology is that an electrolyte system is neutral and environment-friendly, and in addition, the positive electrode and the negative electrode of the technology store electric quantity through an ion intercalation electrochemical reaction or a mixed reaction, so that a few irreversible reactions exist. The electrolyte is divided into lithium ions, sodium ions, potassium ions, zinc ions, calcium ions, aluminum ions and the like or a mixed ion system according to the types of migration ions in the electrolyte, and the saline-water batteries of different systems, such as a water system sodium ion battery, a water system zinc ion battery or a water system calcium ion battery and the like, are formed by matching corresponding anode and cathode materials.
The conventional brine battery structurally comprises a battery unit consisting of positive and negative electrode active substances and a diaphragm, a sealed battery shell and electrolyte filled in the shell. The electrolyte is generally an inorganic salt aqueous solution, and is in a rich state due to the limitation of inorganic salt solubility and the liquid absorption rate of a battery diaphragm, the mass and the volume of the battery are increased by excessive electrolyte load, so that the mass of an inactive substance is higher, and the mass of the battery is heavier under the condition of the same output energy.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a brine battery with a light-weight barren solution structure, which can effectively reduce the weight of the battery and improve the mass specific energy and the volume specific energy of the battery.
The technical scheme for realizing the purpose is as follows: a brine battery with a light-weight barren solution structure comprises an encapsulation film and a battery cell sealed in the encapsulation film; the battery cell is formed by overlapping and assembling an integrated electrode plate soaked with electrolyte and a diaphragm according to a Z shape, wherein the integrated electrode plate consists of a current collector matrix and electrode active substance layers loaded on the upper surface and the lower surface of the current collector matrix;
the current collector substrate is a metal current collector substrate or a non-metal current collector substrate, and the thickness of the metal current collector substrate is 0.01-2.0 mm; the thickness of the nonmetal current collector substrate is 0.5-5.0 mm;
the thickness of the electrode active material layer is 0-3 mm;
the thickness of the diaphragm is 0.2-5 mm.
In the brine battery with the light-weight lean solution structure, the electrode active material layer is loaded on the current collector substrate through a slurry drawing, casting, coating or die pressing process, and the contact between the active material layer and the current collector substrate is increased through multiple times of roller pressing.
The brine battery with the light-weight barren solution structure is characterized in that the integrated electrode plate comprises an integrated positive electrode plate and an integrated negative electrode plate, and the electrode active material layer comprises a positive electrode active material layer and a negative electrode active material layer;
the integrated positive electrode plate consists of a current collector substrate and a positive active material layer loaded on the upper surface and the lower surface of the current collector substrate;
the integrated negative electrode plate consists of a current collector substrate and a negative active material layer loaded on the upper surface and the lower surface of the current collector substrate;
the battery cell is formed by overlapping and assembling an integrated negative electrode plate soaked with electrolyte, a diaphragm and an integrated positive electrode plate in a Z shape.
The brine battery with the light-weight lean solution structure is characterized in that the material of the metal current collector substrate includes, but is not limited to, at least one of an aluminum foil, a copper foil, a nickel strip, a zinc strip, an iron strip and a stainless steel strip;
the shape of the metal current collector matrix adopts foil, woven mesh, punched mesh, grid plate, felt or foam;
the non-metal current collector substrate adopts at least one of flexible graphite, carbon cloth, carbon felt, foam carbon, impregnated graphite and carbon fiber cloth;
the separator may be at least one selected from the group consisting of, but not limited to, a glass fiber separator, a polymer separator, a gel-state separator, and a fibrous nonwoven fabric.
In the brine battery with the light-weight barren solution structure, the width of the diaphragm is 105-110% of the width of the integrated electrode plate.
In the brine battery with the light-weight barren solution structure, the packaging film is an aluminum plastic film or a polymer-metal composite laminated film.
The brine battery with the light-weight barren solution structure is characterized in that the electrolyte is an inorganic brine solution, cations of inorganic salts in the inorganic brine solution comprise at least one of sodium ions, lithium ions, zinc ions, manganese ions, potassium ions, aluminum ions and magnesium ions, and anions comprise at least one of sulfate radicals, phosphate radicals, hydroxyl radicals, acetate radicals, nitrate radicals or perchlorate radicals;
a surfactant is added into the electrolyte, and the mass fraction of the surfactant in the electrolyte is 0.01-5%; the surfactant is anionic surfactant, cationic surfactant, zwitterionic surfactant, nonionic surfactant or organic solvent.
The brine battery with the light weight barren solution structure is characterized in that the anionic surfactant comprises, but is not limited to, stearic acids, higher fatty alcohol or sulfonate;
the cationic surfactants include, but are not limited to, quaternary ammonium compounds;
the zwitterionic surfactants include, but are not limited to, lecithin;
the nonionic surfactants include, but are not limited to, polyoxyethylene type or polyhydric alcohol type;
the organic solvent includes, but is not limited to, methanol, ethanol, isopropanol, or n-butanol.
The brine battery with the light-weight barren solution structure is characterized in that a single brine battery, namely a single battery cell, is assembled by adopting an assembly process of soaking, laminating and packaging, an integrated electrode soaked with electrolyte and a diaphragm are firstly used for laminating and assembling a battery cell, then the assembled battery cell is sealed by adopting a packaging film to form the single battery cell, and the single battery cell is connected in series and parallel according to different energy or power requirements of the battery cell when in use.
The brine battery with the light-weight barren solution structure has the following advantages:
(1) the integrated electrode plate is a close combination of an electrode active substance and a current collector, so that the contact impedance in the battery is greatly reduced, and the high-rate output of the battery pack is favorably realized;
(2) the weight of the packaging film (aluminum plastic film) and the accurate calculation of the electrolyte consumption can greatly improve the mass ratio of active substances in the battery, the structure is compact, and the gas evolution side reaction generated by the decomposition of free water is greatly reduced;
(3) the battery does not need a liquid injection process in the assembly process, so that the assembly process is simpler;
(4) the electrolyte existing in the diaphragm greatly shortens the ion migration distance in the charging and discharging processes, and meanwhile, the surfactant added in the electrolyte can reduce the surface tension of a solid-liquid interface, so that the ion concentration of a reaction interface is kept constant, and high-rate output can be realized;
(5) the sealed packaging film (aluminum plastic film) package can delay the volatilization rate of the electrolyte.
Drawings
Fig. 1 is a structural view of a brine battery of a lightweight lean liquid structure of the present invention;
fig. 2 is a graph comparing the cycle performance of the batteries of comparative example and example.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the following detailed description is given with reference to the accompanying drawings:
referring to fig. 1, according to an embodiment of the present invention, a brine battery with a light-weight lean solution structure includes an encapsulation film (not shown) and a battery cell 100 sealed therein; the battery cell 100 is formed by overlapping and assembling an integrated electrode plate soaked with electrolyte and a diaphragm 4 according to a zigzag shape, wherein the integrated electrode plate is composed of a current collector matrix 1 and electrode active substance layers loaded on the upper surface and the lower surface of the current collector matrix.
The current collector substrate 1 is a metal current collector substrate or a non-metal current collector substrate, and the metal current collector substrate is made of at least one of aluminum foil, copper foil, nickel tape, zinc tape, iron tape and stainless steel tape; the shape of the metal current collector matrix adopts foil, woven mesh, punched mesh, grid plate, felt or foam; the thickness of the base body of the metal current collector 1 is 0.01-2.0 mm; the non-metal current collector substrate is at least one of flexible graphite, carbon cloth, carbon felt, carbon foam, impregnated graphite and carbon fiber cloth, and the thickness of the non-metal current collector substrate is 0.5-5.0 mm; the electrode active substance layer is loaded on the current collector substrate by methods of slurry drawing, tape casting, coating, mould pressing and the like, and the contact between the electrode active substance and the current collector substrate can be increased by multiple times of roller pressing; the thickness of the electrode active material layer is 0-3 mm; the membrane is at least one selected from glass fiber membrane, polymer membrane, gel state membrane and fiber non-woven fabric, and the thickness of the membrane 4 is 0.2-5 mm. And cutting an integrated electrode plate and a diaphragm with required sizes, wherein the width of the diaphragm is 105-110% of that of the integrated electrode plate, so as to prevent the electrodes from being short-circuited. The packaging film adopts an aluminum plastic film or a polymer-metal composite laminated film.
The electrolyte adopts an inorganic salt aqueous solution, cations of inorganic salts in the inorganic salt aqueous solution comprise at least one of sodium ions, lithium ions, zinc ions, manganese ions, potassium ions or magnesium ions, and anions comprise sulfate radicals, phosphate radicals, hydroxide radicals, acetate radicals, nitrate radicals or perchlorate ions; adding a surfactant for reducing the surface tension of a solid-liquid interface and increasing the wettability of the solid-liquid interface into the electrolyte, wherein the mass fraction of the surfactant in the electrolyte is 0.01-5%; the surfactant is anionic surfactant, cationic surfactant, zwitterionic surfactant, nonionic surfactant or organic solvent. Anionic surfactants include, but are not limited to, stearates, higher fatty alcohols, or sulfonates; cationic surfactants include, but are not limited to, quats; zwitterionic surfactants include, but are not limited to, lecithin; nonionic surfactants include, but are not limited to, polyoxyethylene or polyhydric alcohol types; organic solvents include, but are not limited to, methanol, ethanol, isopropanol, or n-butanol.
The following comparative examples and examples were compared using an aqueous sodium ion battery in which the positive electrode active material layer used a manganese-based oxide and the negative electrode active material layer used a titanium phosphorus oxide.
In this embodiment, the integrated electrode sheet includes an integrated positive electrode sheet a and an integrated negative electrode sheet B, and the electrode active material layer includes a positive electrode active material layer 2 and a negative electrode active material layer 3; the integrated positive electrode slice A consists of a current collector matrix 1 and a positive active material layer 2 loaded on the upper surface and the lower surface of the current collector matrix; the integrated negative electrode slice B consists of a current collector matrix 1 and a negative active material layer 3 loaded on the upper surface and the lower surface of the current collector matrix; the battery cell 100 is formed by stacking and assembling an integrated negative electrode plate B soaked in electrolyte, a diaphragm 4 and an integrated positive electrode plate a in a zigzag manner. A stainless steel belt (50 mu m thick) of a punching net is used as a current collector substrate, positive and negative active material layers are attached to the current collector substrate in a slurry drawing mode, and are tightly combined through multiple rolling, and the current collector substrate is cut into an integrated electrode slice of 60mm by 60 mm. According to the calculation of the electrolyte demand, the glass fiber diaphragm with the thickness of 1mm can meet the battery circulation demand, sodium dodecyl benzene sulfonate with the mass fraction of 1% is added to serve as a surfactant, the integrated positive electrode plate, the integrated negative electrode plate and the diaphragm are soaked in the electrolyte for 20min, then the positive electrode plate, the integrated negative electrode plate and the diaphragm are overlapped and assembled into the battery core 100 according to the Z shape, and then the battery core 100 is sealed by an aluminum plastic film and tested.
Comparative example:
the positive and negative active materials are pressed into a positive and negative electrode with the thickness of 120mm by a mould pressing mode, stainless steel with the same thickness (50 mu m) is used as a current collector, a conventionally used polypropylene diaphragm with the thickness of 0.2mm is adopted as the diaphragm, lamination assembly is carried out according to the sequence of 'stainless steel current collector-positive electrode-diaphragm-negative electrode-stainless steel current collector', in order to ensure the close contact of the active materials and the current collector, PVC plates with the thickness of 140mm (L) 140mm (W) 10mm (H) are added on two sides of the battery to be used as a pressurizing device, and the pressurizing device is locked by a screw/nut with the thickness of 6 mm. And (3) placing the assembled battery cell into a 160 mm-160 mm ABS shell, filling electrolyte, sealing and testing.
Referring to fig. 2, the cells of the examples and comparative examples, which were tested using the same test protocol and had a design capacity of 100Wh, were found to have a 30% decrease in the mass and a 45% decrease in the volume of the brine cell of the light weight lean solution structure of the present invention in the case where the cycle performances of the two were substantially identical (see fig. 2), and the results are shown in table 1:
TABLE 1
The invention relates to a brine battery with a light-weight barren solution structure, which adopts a diaphragm with high strength, high liquid absorption rate, acid and alkali resistance and certain thickness, an electrolyte added with a surfactant, combines an integrated electrode matched with the diaphragm, adopts an assembly procedure of 'soaking-lamination-packaging' to assemble a single brine battery, namely a single battery, firstly uses the integrated electrode soaked with the electrolyte and the diaphragm to assemble a battery cell in a lamination way, then seals the assembled battery cell by adopting a packaging film to form the single battery, and connects the single batteries in series and parallel according to different energy or power requirements of the battery cell when in use.
In conclusion, the brine battery with the light-weight barren solution structure can effectively reduce the weight of the battery.
It should be understood by those skilled in the art that the above embodiments are only for illustrating the present invention and are not to be used as a limitation of the present invention, and that changes and modifications to the above described embodiments are within the scope of the claims of the present invention as long as they are within the spirit and scope of the present invention.
Claims (7)
1. A brine battery with a light-weight barren solution structure is characterized by comprising an encapsulation film and a battery cell sealed in the encapsulation film; the integrated electrode plate consists of a current collector substrate and electrode active substance layers loaded on the upper surface and the lower surface of the current collector substrate;
the integrated electrode plate comprises an integrated positive electrode plate and an integrated negative electrode plate, and the electrode active material layer comprises a positive electrode active material layer and a negative electrode active material layer;
the integrated positive electrode plate consists of a current collector substrate and a positive active material layer loaded on the upper surface and the lower surface of the current collector substrate;
the integrated negative electrode plate consists of a current collector substrate and a negative active material layer loaded on the upper surface and the lower surface of the current collector substrate;
the battery cell is formed by superposing and assembling an integrated negative electrode plate, a diaphragm and an integrated positive electrode plate soaked with electrolyte according to a Z shape;
the current collector substrate is a metal current collector substrate or a non-metal current collector substrate, and the thickness of the metal current collector substrate is 0.01-2.0 mm; the thickness of the nonmetal current collector substrate is 0.5-5.0 mm;
the thickness of the electrode active material layer is 0-3 mm;
the thickness of the diaphragm is 0.2-5 mm.
2. The brine cell of claim 1, wherein said electrode active material layer is supported on said current collector substrate by a slip, casting, coating or molding process, and wherein contact between said active material layer and said current collector substrate is increased by multiple pressing.
3. The brine battery with the light weight and lean solution structure as claimed in claim 1, wherein the material of the metal current collector substrate comprises at least one of aluminum foil, copper foil, nickel strip, zinc strip, iron strip and stainless steel strip;
the non-metal current collector matrix adopts at least one of flexible graphite, carbon cloth, carbon felt, foam carbon and impregnated graphite;
the diaphragm adopts at least one of a glass fiber diaphragm, a gel state diaphragm and a fiber non-woven fabric.
4. The brine battery with the light-weight barren solution structure as claimed in claim 1, wherein the width dimension of the diaphragm is 105-110% of the width dimension of the integrated electrode sheet.
5. The brine battery with a light weight barren solution structure as claimed in claim 1, wherein the encapsulation film is a polymer-metal composite laminated film.
6. The brine battery with a light weight barren solution structure as claimed in claim 1, wherein the electrolyte adopts an inorganic salt aqueous solution, cations of inorganic salts in the inorganic salt aqueous solution comprise at least one of sodium ions, lithium ions, zinc ions, manganese ions, potassium ions, aluminum ions and magnesium ions, and anions comprise at least one of sulfate radicals, phosphate radicals, acetate radicals, nitrate radicals and perchlorate radicals;
a surfactant is added into the electrolyte, and the mass fraction of the surfactant in the electrolyte is 0.01-5%; the surfactant is anionic surfactant, cationic surfactant, zwitterionic surfactant or nonionic surfactant.
7. The brine battery with the light weight barren solution structure as claimed in claim 1, wherein a single brine battery, i.e. a single battery cell, is assembled by adopting an assembly process of "soaking-lamination-packaging", a battery cell is assembled by laminating an integrated electrode soaked with electrolyte and a diaphragm, the assembled battery cell is sealed by adopting a packaging film to form the single battery cell, and the single battery cells are connected in series and parallel according to different energy or power requirements of the battery cell when in use.
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