CN115566137A - High-energy-density pole piece, preparation method thereof and battery cell - Google Patents

High-energy-density pole piece, preparation method thereof and battery cell Download PDF

Info

Publication number
CN115566137A
CN115566137A CN202211399589.8A CN202211399589A CN115566137A CN 115566137 A CN115566137 A CN 115566137A CN 202211399589 A CN202211399589 A CN 202211399589A CN 115566137 A CN115566137 A CN 115566137A
Authority
CN
China
Prior art keywords
pole piece
type
active material
energy density
conductive polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202211399589.8A
Other languages
Chinese (zh)
Other versions
CN115566137B (en
Inventor
段利强
程飞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chuneng New Energy Co Ltd
Original Assignee
Chuneng New Energy Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chuneng New Energy Co Ltd filed Critical Chuneng New Energy Co Ltd
Priority to CN202211399589.8A priority Critical patent/CN115566137B/en
Publication of CN115566137A publication Critical patent/CN115566137A/en
Application granted granted Critical
Publication of CN115566137B publication Critical patent/CN115566137B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The invention belongs to the technical field of battery manufacturing, and particularly relates to a high-energy density type pole piece, a preparation method thereof and a battery core. The invention provides a high energy density type pole piece, comprising: the current collector, and from one side or both sides of the current collector outwards set gradually redox type conducting polymer layer, high energy type active material layer. The redox type conductive polymer layer adopts a conjugated polymer with a conjugated structure, the conjugated polymer and a binder are mixed to prepare slurry, the slurry is coated on the foil layer, the speed of electrons entering an active material can be reduced by getting lost electrons during charging, the multiplying power charging of a battery cannot be influenced, and the redox type conductive polymer layer is equivalent to a container for temporarily storing the electrons and gradually releasing the electrons to the active material.

Description

High-energy-density pole piece, preparation method thereof and battery cell
Technical Field
The invention belongs to the technical field of battery manufacturing, and particularly relates to a high-energy density type pole piece, a preparation method thereof and a battery cell.
Background
Various types of batteries have been derived from the rapid development of lithium ion batteries, including fast-charge type lithium ion batteries, high-energy-density type lithium ion batteries, low-cost lithium ion batteries, and ultra-long cycle lithium ion batteries. At present, with the rapid development of electric automobiles, the market requirements on the electric automobiles are more and more strict, and the long endurance mileage needs to be met and the rapid charging needs to be realized. However, the surface area and particle size of the positive and negative electrode materials used in the high energy density type battery have determined that the material cannot realize charge and discharge at a rate of 2C to 10C or more, and the material has low intrinsic conductivity. The fast-charging battery needs to be added with more conductive agents in the preparation process, the active ratio of the main material is lower, and the energy density of the fast-charging battery is far lower than that of the high-energy-density battery. On the other hand, the high energy density type battery has great potential safety hazard caused by lithium precipitation due to overlarge current density in the charging and discharging processes.
The lithium precipitation of the high-energy density battery is a continuous process, and the basic reason is understood to be that when 2C current reaches the copper foil, 2C electrons are generated, and then the lithium ions in the battery electrolyte need 2C amount and an active material to react and neutralize the 2C electrons, but the conductivity of the material can only bear 1C neutralization reaction, and 1C more lithium ions are deposited on the surface of the material. The main reason is that the copper foil has high conductivity and the material has low conductivity, so that lithium ions are not only transported to the whole active space, and excessive lithium ions are accumulated in a region with high current density, and then reaction is carried out to generate lithium precipitation. To address the problem of lithium precipitation, the concentration of lithium ions within the battery is reduced and the rate of current transfer into the active material is limited while the battery is being charged.
Chinese patent CN 111354950A discloses a foil, a preparation method thereof, a battery cell, a battery module and an energy storage device, wherein a conductive polymer is doped with lithium salt and coated on a current collector, and mutual conversion between conductivity and insulation is realized by doping and dedoping of the lithium salt, so that an electronic channel between the foil and an active material can be cut off, and overcharge and overdischarge are prevented. However, this method cannot achieve high-rate charge and discharge with high energy density, and cannot solve the problem of lithium precipitation of the battery.
Therefore, finding a method which can improve the quick charge performance of the lithium ion battery and can not reduce the energy density of the battery is an urgent problem to be solved in the field of secondary batteries.
Disclosure of Invention
The invention provides a high-energy-density pole piece, a preparation method thereof and a battery cell, and aims to solve the problems that in the prior art, a high-energy-density battery cannot realize high-rate charge and discharge and lithium precipitation of the battery under the high-rate charge condition.
In view of the above technical defects, an object of the present invention is to provide a high energy density type pole piece, an object of the present invention is to provide a method for manufacturing the high energy density type pole piece, and an object of the present invention is to provide a battery cell including the high energy density type pole piece.
In a first aspect, the present invention provides a high energy density type pole piece, comprising: the current collector, and from the redox type conducting polymer layer, the high energy type active material layer that set gradually outward from a side or both sides of current collector.
In the above-described high energy density type pole piece, as a preferred embodiment, the conductive polymer in the redox type conductive polymer layer is a doped conjugated polymer of polyacetylene, polypyrrole, polythiophene or polyaniline;
the dopant in the doped conjugated polymer is preferably iodine vapor, protonic acid, arsenic pentoxide, lithium naphthyl or sodium naphthyl;
the mole percentage of the dopant in the doped conjugated polymer is 5-50% (e.g., 15%, 25%, 35%, 45%), preferably 10-30%.
Preferably, the conductive polymer has a conductivity of 10 to 10 6 S/cm (e.g., 10) 2 S/cm、10 3 S/cm、10 4 S/cm、10 5 S/cm); but are not limited to only those listedTo take numerical values, other numerical values not recited in the numerical range are equally applicable.
In the above-mentioned high energy density type pole piece, as a preferable real-time mode, the thickness of the redox type conductive polymer layer is 1 to 100 μm (for example, 10 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm), preferably 5 to 20 μm;
and/or the thickness of the high energy density type pole piece is 50-200 μm (for example, 70 μm, 90 μm, 110 μm, 130 μm, 150 μm, 170 μm, 190 μm).
In the above high energy density type pole piece, as a preferable embodiment, the active material of the high energy type active material layer is a graphite-based or/and carbon silicon-based high energy type active material. Preferably a high energy type active material with a theoretical energy density of more than 140 mAh/g. The graphite-based high-energy active material is artificial graphite.
In the above-described high energy density type pole piece, as a preferred embodiment, the redox type conductive polymer layer is obtained by applying a conductive polymer-containing glue solution onto a current collector, drying, and rolling.
In one embodiment of the present invention, the high energy type active material layer is obtained by applying a slurry containing a high energy density type active material onto the redox type conductive polymer layer, drying, and rolling.
In one embodiment of the present invention, the current collector has a thickness of 4.5 to 8 μm (e.g., 5 μm, 7 μm).
In one embodiment of the present invention, the redox conductive polymer layer and the high-energy type active material layer are prepared by performing rolling at a compaction ratio (i.e., pre-rolling thickness/post-rolling thickness = 1.2-1.8) of 1.2-1.8 (e.g., 1.3, 1.4, 1.6, 1.7).
In a second aspect, the invention further provides a method for preparing the high energy density type pole piece, which comprises the following steps,
s1: coating the glue solution containing the conductive polymer on one side or two sides of the current collector, and drying and rolling to obtain the current collector with the redox type conductive polymer layer;
s2: and coating slurry containing the active material of the high-energy active material layer on the redox type conductive polymer layer, and drying and rolling to obtain the high-energy density type pole piece.
In the above method for manufacturing a high energy density type pole piece, as a preferred embodiment, in S1, the coating method of the adhesive solution containing a conductive polymer is one of micro gravure coating, and slot coating;
and/or the coating thickness of the conductive polymer glue solution is 1-100 μm (such as 10-30 μm, 40-50 μm, 60-70 μm, 80-90 μm), and more preferably 5-20 μm;
and/or the solid content of the glue solution containing the conductive polymer is 55-70% (such as 50%, 60%, 65%, 70%); the solid content here is the mass content;
and/or the glue solution containing the conductive polymer comprises a redox type conductive polymer, a first binder and a first solvent.
More preferably, the mass ratio of the redox conductive polymer to the first binder is (95-100): (0-5), and the sum of the proportion of the two is 100;
and/or the first solvent comprises deionized water, acetonitrile, methanol and N-methylpyrrolidone;
and/or the first binder is one or more of sodium carboxymethylcellulose (SBR), styrene butadiene rubber (CMC), polyvinylidene fluoride (PVDF) and polyethylene oxide (PEO); the adhesive used for preparing the conductive polymer paste includes, but is not limited to, the above-mentioned adhesives, and adhesives having the same adhesive function may be applied to the present invention.
In the preparation method of the redox type conductive polymer layer, the addition amount of the first solvent can be calculated according to the solid content of the conductive polymer glue solution, the mass of the redox type conductive polymer and the mass of the binder.
In the above method for manufacturing a high energy density type pole piece, as a preferred embodiment, the slurry containing the active material of the high energy type active material layer further includes a conductive agent, a second binder, and a second solvent. The types and the dosage relationship of the conductive agent, the second binder and the second solvent can be adjusted according to the types of the active materials, and are conventional technologies, and are not described herein again.
In a third aspect, the present invention further provides a battery cell, including multiple negative electrode plates, multiple diaphragms, and multiple positive electrode plates, where the negative electrode plates and the positive electrode plates are alternately arranged, and a diaphragm is arranged between each positive electrode plate and each negative electrode plate, where the negative electrode plates include the above-mentioned high energy density type electrode plate and fast charge type electrode plate, and a rate of an active material of the fast charge type electrode plate is greater than a rate of an active material of the high energy density type electrode plate.
In the above battery cell, as a preferred embodiment, the number of the fast charge type pole pieces satisfies the following formula:
n 0 ＝N(C 2 -C 1 )/(C 3 +C 2 -C 1 )；
wherein n is 0 The number of quick-charging pole pieces in the battery cell, N is the total number of negative pole pieces in the battery cell, C 2 Is the actual multiplying power of the cell, C 1 The maximum bearing multiplying power, C, of the high energy density type pole piece in the battery cell 3 The maximum bearing multiplying power of the quick-charging type pole piece is realized.
In the present invention, n 0 And (4) taking an integer, and when the decimal number exists in the actual calculation result, directly taking the integer part or adding 1 to the integer part without considering the numerical value after the decimal point.
According to the invention, by setting the number of the quick-charging pole pieces in the battery cell, the high-rate charging and discharging can be carried out under the condition that the energy density of the battery cell is not influenced.
In the battery cell, as a preferred embodiment, the fast charging pole pieces are uniformly distributed in the battery cell.
In the battery cell, as a preferred embodiment, the battery cell includes a plurality of cells and a first positive electrode sheet disposed between adjacent cells; each single body comprises one fast charging type pole piece, a second positive pole piece and a high energy density type pole piece, wherein the second positive pole piece and the high energy density type pole piece are arranged on two sides of the fast charging type pole piece, the number of the second positive pole piece and the high energy density type pole piece on one side of the fast charging type pole piece in the single body is the same, and the number of the pole pieces on two sides of the fast charging type pole piece is the same or similar (for example, in the single body, the difference between the total number of the pole pieces on one side and the total number of the pole pieces on the other side is 2 or 4, and when the difference is 2, one side is less than the other side by one second positive pole piece and one high energy density type pole piece); the second positive pole pieces and the negative pole pieces are alternately arranged, and second diaphragms are arranged between the adjacent second positive pole pieces and the adjacent negative pole pieces; a first diaphragm is also arranged between the adjacent monomer and the first positive pole piece.
In order to clearly express the preferred structure of the battery cell, in the preferred battery cell structure, the positive pole piece is divided into a second positive pole piece positioned in the monomer and a first positive pole piece positioned outside the monomer according to the position difference of the positive pole piece, and the preparation methods of the positive pole pieces at different positions are the same as those of the active material; dividing the diaphragm into a second diaphragm positioned in the monomer and a first diaphragm positioned outside the monomer according to different positions of the diaphragm, wherein the preparation methods and materials of the diaphragms at different positions are the same; the negative pole piece comprises a quick-charging pole piece and a high-energy-density pole piece.
In the battery cell, as a preferred embodiment, the ratio of the thicknesses of the active material layer of the fast charge type pole piece and the active material layer of the high energy density type pole piece is (1-1.5): 1;
the thickness of the high-energy density pole piece is 50-200 μm.
In the battery cell, as a preferred embodiment, the active material of the fast-charging type pole piece is a graphite-based or/and carbon-silicon-based fast-charging type active material; the graphite-based rapid-filling active material is preferably hard carbon or/and soft carbon. The multiplying power of the active material of the quick-charging type pole piece is 1-50C, and preferably 1-5C.
In the battery cell, as a preferred embodiment, the difference between the active material rate of the fast charge type pole piece and the active material rate of the high energy density type pole piece is 0.2C-2C, preferably 0.2C-1C; for example, the maximum charge-discharge multiplying power of the high-energy active material layer active material is 0.33C, and the multiplying power of the quick-charge pole piece active material is 0.83C-1.33C. The difference of the two times is in the preferable range of the invention, so that the concentration difference can be better constructed, and the condition of lithium precipitation is ensured not to occur. When the multiplying power difference is too large, the fast-charging type pole piece can be subjected to lithium precipitation, and when the multiplying power difference is too small, the concentration difference cannot be constructed, and the effect of the fast-charging type pole piece cannot be exerted without the concentration difference.
In some embodiments of the present invention, the fast charging type electrode sheet is prepared according to a conventional preparation process of a negative electrode sheet, for example, an active material, a conductive agent, a binder and a solvent of the fast charging type electrode sheet are made into slurry, and then the slurry is coated on a current collector.
In some embodiments of the present invention, the coating of the active material of the fast-charging pole piece and the active material of the high-energy active material layer can be performed by one of extrusion coating, transfer coating or spraying.
The battery core can be of a winding type or a laminated type. The cells of the invention may also include conventional components of electrolyte/solid electrolyte, housing, and the like.
The active material of the positive pole piece of the battery core can be common positive active materials of secondary batteries, and the invention is preferably the positive active material of a lithium battery, such as ternary materials of lithium iron phosphate, lithium cobalt phosphate, lithium iron manganese phosphate or lithium nickel cobalt manganese phosphate. The positive pole piece can be prepared by a conventional wet method or a dry method.
In the battery cell of the invention, the high energy density type pole piece and the quick charge type pole piece are both used as a negative electrode, and the current collector is preferably a copper foil.
Compared with the prior art, the invention has at least one of the following beneficial effects:
1. the redox type conductive polymer layer adopts conjugated polymer with a conjugated structure, the conjugated polymer and the binder are mixed to prepare slurry, the slurry is coated on the foil layer, the speed of electrons entering an active material can be reduced by getting lost electrons during charging, the rate charging of a battery cannot be influenced, and the redox type conductive polymer layer is equivalent to a container for temporarily storing the electrons and gradually releasing the electrons to the active material.
2. The redox type conductive polymer provided by the invention can combine electrons at a low potential, can gradually release the electrons along with the gradual rise of the potential, and can effectively decompose the chemical reaction of a high-energy density type active material, thereby improving the rate capability, namely the quick charging performance of the high-energy density type active material.
3. The invention provides a battery cell, wherein a fast-charging type pole piece is inserted into the battery cell, the fast-charging type pole piece can be quickly combined with lithium ions, a lithium ion concentration gradient is constructed between the fast-charging type pole piece and a high-energy density type pole piece, and the lithium ion concentration on the surface of the high-energy density type pole piece is reduced, so that the possibility of lithium precipitation of the high-energy density type pole piece is effectively reduced, and the fast-charging performance of a battery is improved.
4. According to the invention, the structure of the battery cell is optimized, the quick-charging type pole piece is added with the active material pole piece, the quick-charging type pole piece and the high-energy density type pole piece are made into the battery cell, the quick-charging type pole piece can be quickly combined with lithium ions during high-power charging so as to consume lithium in electrolyte, and the lithium ions can slow down the moving speed to the high-energy density type pole piece under the action of concentration difference.
Drawings
FIG. 1 is a schematic structural diagram of a high energy density type pole piece prepared by the present invention;
fig. 2 is a schematic structural view of a cell unit prepared in example 1;
fig. 3 is a schematic view of the overall structure of a battery cell prepared in example 1;
FIG. 4 is a schematic diagram showing the operation of a redox type conductive polymer in example 1;
FIG. 5 is a schematic diagram of the working principle of a negative electrode plate, wherein (a) is a schematic diagram of the working principle between a fast charging type electrode plate and a high energy density type electrode plate in the charging and discharging process; (b) Is a schematic diagram of the working principle of high energy density type pole pieces in the charging and discharging process;
fig. 6 is an exploded view of a cell after the cell is cycled for 100 cycles in example 1;
fig. 7 is a schematic structural view of one of the cell units prepared in example 2;
fig. 8 is an exploded view of the cell of comparative example 1 after the cell has been cycled for 100 cycles.
The reference numbers are as follows:
1-high energy density type pole piece; 2-quick charge pole piece; 3-positive pole piece; 4-a layer of high energy type active material; a 5-redox type conductive polymer layer; 6-layer of foil (current collector); 7-quick-fill active material layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiments of the present invention are implemented on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following embodiments, and the following embodiments do not indicate process parameters of specific conditions, and generally follow conventional conditions.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value and should be understood to encompass values close to these ranges or values. For numerical ranges, combinations of values between the endpoints of each of the ranges, between the endpoints of each of the ranges and individual values, and between the individual values can result in one or more new numerical ranges, and such numerical ranges should be considered as being specifically disclosed herein.
Example 1
The embodiment provides a method for preparing a redox type conductive polymer layer on a current collector, which comprises the following steps:
(1) The conductivity is selected to be 10 4 S/cm redox type polyacetylene (dopant is iodine, and the mole ratio of iodine to polyacetylene is 10%) is used as redox type conductive polymer. The mass ratio of polyacetylene to styrene butadiene rubber (CMC) is 96:4.firstly, calculating the content of deionized water according to 65% of the solid content of the conductive polymer glue solution, then completely adding styrene butadiene rubber and deionized water into a stirring tank, stirring at 3000rpm for 120min, adding polyacetylene, and stirring at 3500rpm for 90min to obtain the conductive polymer glue solution.
(2) The conductive polymer glue solution is coated on both sides of a copper foil (with the thickness of 6 mu m) by using a micro gravure coater, and a current collector with a redox type conductive polymer layer with the thickness of 20 mu m, namely a composite current collector, is obtained after drying and rolling, wherein the thickness of the composite current collector is 26 mu m.
The embodiment also provides a high-energy density type pole piece and a preparation method thereof, and the preparation method comprises the following steps:
the artificial graphite is selected as an active material of the high-energy density type pole piece, and the charge-discharge multiplying power of the pole piece is 0.5C. Mixing artificial graphite, a binder CMC and a conductive agent SP according to a ratio of 96.5:2:1.5, coating the redox type conductive polymer layer with a paste prepared by adopting a squeeze coating mode, drying and rolling to obtain the high-energy density type pole piece, wherein the thickness of the single-sided high-energy type active material layer is 58 mu m (namely the total thickness of the two-sided high-energy type active material layers is 116 mu m). The specific structure of the high energy density type pole piece is shown in fig. 1, and comprises a foil layer 6, redox type conductive polymer layers 5 arranged on two side faces of the foil layer 6, and a high energy type active material layer 4 arranged on the surface of the redox type conductive polymer layer 5. The thickness of the high energy density type pole piece is 142 μm.
The embodiment also provides a preparation method of the quick-charging type pole piece, which comprises the following steps:
hard carbon is selected as an active material of the quick-charging type pole piece, and the charge-discharge multiplying power of the quick-charging type pole piece is 2C. Mixing hard carbon, a binder CMC and a conductive agent SP according to the proportion of 95.5:2.5:2, coating the paste on two side surfaces of a copper foil (the thickness is 6 mu m) in an extrusion coating mode, drying and rolling to obtain the quick-filling pole piece, wherein the thickness of the active material layer is 58 mu m. The thickness of the fast-charging pole piece is 122 μm.
The preparation method of the positive plate comprises the following steps: lithium iron phosphate, a conductive agent SP and a binder PVDF are mixed according to the weight ratio of 96.8:2:1.2, coating the slurry on two surfaces of an aluminum foil, drying and rolling to obtain the positive plate.
The embodiment also provides a battery cell which is basically composed of a positive plate, a negative plate and a diaphragm. The negative pole piece comprises two high-energy-density pole pieces and a quick-charging pole piece which are prepared in the embodiment, and the negative pole piece is prepared according to a formula: n is a radical of an alkyl radical 0 ＝N(C 2 -C 1 )/(C 3 +C 2 -C 1 ) The total number of layers of the battery cell negative pole pieces is 20, and the actual multiplying power C of the battery cell 2 1C, the maximum bearing rate C of the high-energy density type pole piece 1 0.5C, the maximum bearing multiplying power C of the quick-charging type pole piece 3 Is 2C. And 4 fast charging pole pieces are calculated according to a formula. Fig. 2 and 3 are schematic diagrams of cell structures, where fig. 2 shows a single structure in a cell, that is, two sides of a fast charging type pole piece 2 are respectively provided with 2 high energy density type pole pieces 1 and 2 positive pole pieces 3, the positive and negative pole pieces 3 are alternately arranged and a diaphragm (not shown in the figure) is arranged between adjacent pole pieces, specifically, two sides of the fast charging type pole piece 2 are stacked with diaphragms, then the positive pole piece 3 is stacked on the diaphragms, then the diaphragms are stacked on the positive pole piece 3, then the high energy density type pole pieces 1 are stacked on the diaphragms, and then the diaphragms, the positive pole pieces 3, the diaphragms and the high energy density type pole pieces 1 are sequentially stacked on the diaphragms, the whole cell is a unit of the cell, the whole cell comprises four pole piece units according to the unit stack, the positive pole pieces 3 are arranged between the units, and the diaphragms are stacked on two sides of the positive pole pieces 3 between the units, thereby forming a basic structure of the whole cell, see fig. 3. Of course, the necessary electrolyte and shell are also included in the battery core, the electrolyte and shell can be the conventional electrolyte and shell of a lithium ion battery, and the electrolyte of the electrolyte used in the embodiment is LiPF 6 The solvent is Ethylene Carbonate (EC) and dimethyl carbonate (DMC) with the volume ratio of 1. The theoretical capacity of the obtained cell was 20Ah.
As shown in FIG. 4, the redox type conductive polymer in the cell operates on the principle that the electrons of the external circuit first flow through the foil, the conductivity of the foil (10) 6 S/cm) is very high and almost does not form resistance to electronsThe conductive polymer has excellent conductivity, and although the conductivity is not as good as that of a foil, since the conductive polymer is a redox type polymer and has a conjugated structure, electrons can be obtained and lost through redox, the electron transfer rate is relatively reduced, but the number of the electrons is not reduced. In the initial charging stage, the voltage of the battery cell is reduced compared with the lower conductive polymer through n-type doping, the conductive polymer firstly contains part of electrons, part of the electrons are transmitted to the high-energy type active material layer 4, the number of the electrons received by the active material is reduced, the number of corresponding lithium ions is reduced, and the high-energy density type pole piece 1 can sufficiently process the lithium ions according to the multiplying power of the high-energy density type pole piece 1 without lithium precipitation. As the voltage is increased, the conductive polymer undergoes p-type doping and is oxidized to lose electrons to the high energy type active material layer 4. The redox conductive polymer layer 5 serves as an electron storage device and temporarily stores electrons in the system, but does not reduce the number of electrons in the system and does not reduce the rate capability of the cell.
As shown in fig. 5, lithium ion transport between the rapid charging type pole piece 2 and the high energy density type pole piece 1 does not overlap the role of the redox type conductive polymer layer. The positive electrode loses lithium ions into the electrolyte during charging, after which the lithium ions move from the positive electrode to the negative electrode and react with the negative electrode. Under a large multiplying power, if the multiplying power of the negative electrode is lower than the charging multiplying power, the consumption of lithium ions in the electrolyte is in a non-equilibrium state, the concentration of the lithium ions is increased rapidly, and the lithium ions are deposited on the surface of the negative electrode material rapidly under the action of an electric field to cause lithium precipitation. The fast charge type negative pole piece has a relatively large charge rate, lithium ions around the pole piece can be consumed rapidly in the charging process, it can be seen from fig. 5 (b) that the lithium ion concentration of the battery cell without the fast charge type negative pole piece is relatively uniform, and the battery cell with the fast charge type negative pole piece refers to fig. 5 (a), and the lithium ions around the high-energy density type pole piece can gradually move towards the negative pole of the fast charge type pole piece under the action of concentration difference and the driving of an electric field due to the reduction of the lithium ion concentration around the fast charge type pole piece, so that the lithium ion concentration around the high-energy type negative pole piece is reduced, and the risk of lithium precipitation is reduced.
The performance of the battery cell assembled in this embodiment is tested, and the specific test method is as follows: the first scheme is as follows: under the condition of normal temperature of 25 ℃, the charging step is to charge the battery to 3.65V with the multiplying power of 1C under constant current and constant voltage, the discharging step is to discharge the battery to 2.5V with the constant current of 0.5C, and after 100 cycles, the battery core is disassembled to check whether lithium is separated out from the surface of the pole piece. Simultaneously, a second scheme is set: charging to 3.65V at constant current and constant voltage of 0.5C in the charging step, discharging to 2.5V at constant current of 0.5C in the discharging step, and disassembling the cell to check the contrast test of whether lithium is separated from the surface of the pole piece after 100 cycles.
Under the action of the conductive polymer layer and the fast-charging type negative plate, the rate performance of the battery is obviously improved, the improvement from 0.5C to 1C can be completely realized, and as shown in fig. 6, after 100 cycles, the battery core is disassembled to find that no lithium precipitation occurs on the surface of the pole piece, and the specific result is shown in table 1.
Example 2
The embodiment provides a method for preparing a redox type conductive polymer layer on a current collector, which comprises the following steps:
(1) The conductivity is selected to be 10 3 S/cm redox type polyaniline (dopant is protonic acid, and the mol ratio of protonic acid to polyaniline is 15%). The mass ratio of polyaniline to polyethylene oxide (PEO) was 95:5.
firstly, calculating the content of N-methylpyrrolidone (NMP) according to 70% of the solid content of the conductive polymer glue solution, then adding polyoxyethylene and N-methylpyrrolidone into a stirring tank, stirring at 3500rpm for 100min, adding polyaniline, and stirring at 4000rpm for 110min to obtain the conductive polymer glue solution.
(2) The conductive polymer glue solution is coated on two sides of a copper foil (with the thickness of 6 mu m) by using a micro gravure coater, and a current collector with a redox type conductive polymer layer with the thickness of 25 mu m, namely a composite current collector, is obtained after drying and rolling, wherein the thickness of the composite current collector is 31 mu m.
The embodiment also provides a high-energy density type pole piece and a preparation method thereof, and the preparation method comprises the following steps:
the artificial graphite is selected as an active material of the high-energy density type pole piece, and the charge-discharge multiplying power of the artificial graphite is 1C. Mixing artificial graphite, a binder CMC and a conductive agent SP according to a ratio of 96:2:2, coating the redox type conductive polymer layer with a slurry prepared by adopting a squeezing coating mode, drying and rolling to obtain the high-energy density type pole piece, wherein the thickness of the single-side high-energy type active material layer is 50 microns. The thickness of the high energy density type pole piece is 131 μm. The specific structure of the high energy density type pole piece is shown in fig. 1.
The embodiment also provides a preparation method of the quick-charging type pole piece, which comprises the following steps:
silica graphite is selected as an active material of the fast-charging pole piece, and the charge-discharge multiplying power of the fast-charging pole piece is 3C. Silica graphite (compounded by 30 percent of silica and 70 percent of graphite) and a binder CMC and a conductive agent SP are mixed according to the proportion of 95:3:2, coating the paste on two side surfaces of a copper foil (with the thickness of 6 mu m) in an extrusion coating mode, drying and rolling to obtain the quick-filling pole piece, wherein the thickness of the single-side active material layer is 55 mu m. The thickness of the fast-charging pole piece is 116 μm.
The preparation method of the positive plate comprises the following steps: lithium iron phosphate, a conductive agent SP and a binder PVDF are mixed according to the weight ratio of 96.8:2:1.2, preparing slurry, coating the slurry on two surfaces of an aluminum foil, drying and rolling to obtain the positive plate.
The embodiment also provides a battery cell, which basically comprises a positive plate, a negative plate and a diaphragm, wherein the negative plate comprises two high-energy-density pole pieces and a quick-charging pole piece prepared in the embodiment. According to the formula: n is 0 ＝N(C 2 -C 1 )/(C 3 +C 2 -C 1 ) The total number of layers of the cell negative plate is 30, and the actual multiplying power C of the cell 2 2C, the maximum bearing rate C of the high-energy density type pole piece 1 Is 1C, the maximum bearing multiplying power C of the quick-charging type pole piece 3 Is 3C. And 7 fast charging pole pieces are calculated according to a formula. As shown in the schematic diagram of the cell unit structure shown in fig. 7, two sides of the fast charging type pole piece 2 are respectively provided with 3 high energy density type pole pieces 1 and 3 positive pole pieces 3, and since the number of the high energy density type pole pieces is 23, it cannot be ensured that two sides of each fast charging type pole piece 2 are respectively provided with 3 high energy density type pole pieces 1 and 3 positive pole pieces 3Energy density type pole piece, so can't satisfy 3 high energy density type pole pieces to one of them quick charge type pole piece 2 unilateral, can change into 2 high energy density type pole pieces 1 and 2 positive pole pieces 3, have three electric core unit promptly that there are 3 high energy density type pole pieces 1 and 3 positive pole pieces 3 respectively on quick charge type pole piece 2 both sides, have one electric core unit that one side of quick charge type pole piece 2 has 3 high energy density type pole pieces 1 and 3 positive pole pieces 3, the opposite side has 2 high energy density type pole pieces 1 and 2 positive pole pieces 3. The whole cell is laminated according to the unit. Specifically, the whole battery cell comprises four units, a positive pole piece 3 is arranged between the units, and diaphragms are superposed on two sides of the positive pole piece 3 between the units, so that the basic structure of the whole battery cell is formed. Of course, the necessary electrolyte and shell are also included in the battery core, the electrolyte and shell can be the conventional electrolyte and shell of a lithium ion battery, and the electrolyte of the electrolyte used in the embodiment is LiPF 6 The solvent is Ethylene Carbonate (EC) and dimethyl carbonate (DMC) with the volume ratio of 1. The theoretical capacity of the obtained cell was 35Ah.
The performance of the battery cell assembled in this embodiment is tested, and the specific test method is as follows: the first scheme is as follows: under the condition of normal temperature of 25 ℃, the charging step is to charge the lithium to 3.65V with the multiplying power of 2C under constant current and constant voltage, the discharging step is to discharge the lithium to 2.5V with the constant current of 0.5C, and after 100 cycles, the battery core is disassembled to check whether the lithium is separated out from the surface of the pole piece. Simultaneously, a second scheme is set: in the charging step, the constant current and the constant voltage of 1C are charged to 3.65V, in the discharging step, the constant current of 0.5C is discharged to 2.5V, after 100 cycles, the cell is disassembled to check the contrast test whether the lithium is separated from the surface of the pole piece.
In this embodiment, the conductive polymer with small conductivity is used because PEO is a conductive adhesive, which can play a role of conducting electrons, and the conductive polymer layer is coated thickly, and a fast-charging type pole piece with a larger rate is used, which can effectively improve the actual rate of the battery cell without lithium precipitation, and the specific results are shown in table 1.
Comparative example 1
This comparative example is the same as example 1 except that there is no redox conductive polymer layer and no fast-charging type negative electrode sheet. In the cell structure, the quick-charging type negative pole piece is replaced by a high-energy density type pole piece.
The cell performance test was the same as in example 1.
As shown in fig. 8, after 100 cycles, the cell is disassembled to find that lithium deposition occurs on the surface of the pole piece, and the specific results are shown in table 1.
Comparative example 2
The comparative example is the same as example 1, except that no fast-charging type pole piece is provided, and in the cell structure, the fast-charging type negative pole piece is replaced by a high-energy density type pole piece.
The cell performance was tested as in example 1.
After 100 cycles, the disassembled battery finds that small areas exist on the surface of the pole piece for lithium separation, mainly because the concentration of lithium ions on the surface of the high-energy density pole piece is too high, the risk of lithium separation is increased, and specific results are shown in table 1.
Comparative example 3
This comparative example is the same as example 1 except that the redox type conductive polymer layer is not present.
The cell performance test was the same as in example 1.
After 100 cycles, the disassembled battery finds that lithium is separated from the surface of the pole piece, but the lithium separation degree is lower than that of the comparative example 1, and the specific results are shown in table 1.
Table 1 summary of battery disassembly results at different test rates
Figure BDA0003934451820000151
The test summary results in table 1 show that the combination of the conductive polymer layer and the fast charging type pole piece can buffer the concentration of the lithium ion battery on the surface of the high-energy type pole piece during high-rate charging, and can play a role in improving the rate of the battery.
The above description is only exemplary of the invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the invention is intended to be covered by the appended claims.

Claims (10)

1. A high energy density pole piece, comprising: the current collector, and from the current collector side or two sides outwards set gradually redox type conducting polymer layer, high energy type active material layer, wherein, the conductivity of the conducting polymer in redox type conducting polymer layer is 10-10 6 S/cm。
2. The high energy density type pole piece according to claim 1, wherein the conductive polymer in the redox type conductive polymer layer is a doped conjugated polymer of polyacetylene, polypyrrole, polythiophene or polyaniline;
and/or the redox-type conductive polymer layer has a thickness of 1-100 μm;
and/or the active material of the high-energy type active material layer is graphite-based or/and carbon-silicon-based high-energy type active material.
3. The pole piece of claim 2, wherein the pole piece is a high energy density pole piece,
the dopant in the doped conjugated polymer is iodine vapor, protonic acid, arsenic pentoxide, lithium naphthyl or sodium naphthyl; the mole percentage of the dopant in the doped conjugated polymer is 5-50%;
and/or the thickness of the high energy density type pole piece is 50-200 μm;
and/or the theoretical energy density of the active material of the high-energy active material layer reaches 140mAh/g or more.
4. A method for preparing a high energy density type pole piece according to any one of claims 1 to 3, comprising the following steps:
s1: coating the glue solution containing the conductive polymer on one side or two sides of the current collector, and drying and rolling to obtain the current collector with the redox type conductive polymer layer;
s2: and coating slurry containing the active material of the high-energy active material layer on the redox type conductive polymer layer, and drying and rolling to obtain the high-energy density type pole piece.
5. The method for preparing the high energy density type pole piece according to claim 4, wherein in S1, the coating mode of the glue solution containing the conductive polymer is one of micro-gravure coating, gravure coating and slot coating;
and/or the coating thickness of the conductive polymer glue solution is 1-100 μm;
and/or the solid content of the glue solution containing the conductive polymer is 55-70%;
and/or the glue solution containing the conductive polymer comprises a redox conductive polymer, a first binder and a first solvent; the mass ratio of the redox type conductive polymer to the first binder is (95-100): (0-5), and the sum of the proportion of the two is 100.
6. The method for preparing a high energy density type pole piece according to claim 5, wherein the first solvent comprises deionized water, acetonitrile, methanol and N-methylpyrrolidone;
and/or the first binder is one or more of sodium carboxymethylcellulose, styrene butadiene rubber, polyvinylidene fluoride and polyethylene oxide.
7. A battery core is characterized by comprising a plurality of negative pole pieces, a plurality of diaphragms and a plurality of positive pole pieces, wherein the negative pole pieces and the positive pole pieces are alternately arranged, and the diaphragms are arranged between each positive pole piece and each negative pole piece;
the negative pole piece comprises the high-energy-density pole piece and the quick-charging pole piece according to any one of claims 1 to 3, and the multiplying power of an active material of the quick-charging pole piece is greater than that of the high-energy-density pole piece.
8. The electrical core of claim 7, wherein the number of fast-charging pole pieces satisfies the following formula:
n 0 ＝N(C 2 -C 1 )/(C 3 +C 2 -C 1 )；
wherein n is 0 The number of the quick-charging pole pieces in the battery cell, N is the total number of the negative pole pieces in the battery cell, C 2 Is the actual multiplying power of the cell, C 1 The maximum bearing multiplying power, C, of the high energy density type pole piece in the battery cell 3 The maximum bearing multiplying power of the quick-charging type pole piece is obtained;
and/or the fast charging pole pieces are uniformly distributed in the battery cell;
and/or the difference between the active material multiplying power of the fast-charging type pole piece and the active material multiplying power of the high-energy density type pole piece is 0.2C-2C.
9. The cell of claim 7 or 8, wherein the cell comprises a plurality of cells and a first positive pole piece disposed between adjacent cells; each single body comprises one fast charging type pole piece, and a second positive pole piece and a high-energy density type pole piece which are arranged on two sides of the fast charging type pole piece, wherein in the single body, the number of the second positive pole piece on one side of the fast charging type pole piece is the same as that of the high-energy density type pole piece, and the number of the pole pieces on two sides of the fast charging type pole piece is the same or similar; the second positive pole pieces and the negative pole pieces are alternately arranged, and second diaphragms are arranged between the adjacent second positive pole pieces and the adjacent negative pole pieces; a first diaphragm is also arranged between the adjacent monomer and the first positive pole piece.
10. The cell of claim 7 or 8,
the active material of the fast-charging type pole piece is graphite or/and carbon-silicon fast-charging type active material; the multiplying power of the active material of the quick charge type pole piece is 1-50C;
and/or the difference between the active material multiplying power of the fast-charging type pole piece and the active material multiplying power of the high-energy density type pole piece is 0.2C-1C.
CN202211399589.8A 2022-11-09 2022-11-09 High-energy-density pole piece, preparation method thereof and battery cell Active CN115566137B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211399589.8A CN115566137B (en) 2022-11-09 2022-11-09 High-energy-density pole piece, preparation method thereof and battery cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211399589.8A CN115566137B (en) 2022-11-09 2022-11-09 High-energy-density pole piece, preparation method thereof and battery cell

Publications (2)

Publication Number Publication Date
CN115566137A true CN115566137A (en) 2023-01-03
CN115566137B CN115566137B (en) 2023-05-26

Family

ID=84768206

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211399589.8A Active CN115566137B (en) 2022-11-09 2022-11-09 High-energy-density pole piece, preparation method thereof and battery cell

Country Status (1)

Country Link
CN (1) CN115566137B (en)

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002198034A (en) * 2000-12-26 2002-07-12 Shin Kobe Electric Mach Co Ltd Nonaqueous electrolyte secondary cell
CN101373826A (en) * 2007-08-24 2009-02-25 比亚迪股份有限公司 Silicium cathode and lithium ion secondary battery containing the same, and method for preparing the same
CN104916809A (en) * 2014-03-12 2015-09-16 中国科学院金属研究所 Integrated flexible electrode
CN109755557A (en) * 2019-01-04 2019-05-14 桑顿新能源科技有限公司 A kind of safe high-voltage high-energy-density lithium ion battery and preparation method thereof
JP2019153404A (en) * 2018-03-01 2019-09-12 国立研究開発法人物質・材料研究機構 Negative electrode for secondary battery, manufacturing method thereof, and secondary battery using the same
CN110556511A (en) * 2019-09-03 2019-12-10 珠海格力电器股份有限公司 Lithium battery negative pole piece with excellent cycle performance, preparation method thereof and lithium ion battery
JP2020009916A (en) * 2018-07-09 2020-01-16 サン電子工業株式会社 Electrolytic capacitor and electronic apparatus using the same
CN110943215A (en) * 2019-05-31 2020-03-31 宁德时代新能源科技股份有限公司 Lithium ion secondary battery
CN112103471A (en) * 2020-09-08 2020-12-18 东莞维科电池有限公司 Pole piece and lithium ion battery
CN112349910A (en) * 2019-04-28 2021-02-09 宁德时代新能源科技股份有限公司 Negative current collector, negative pole piece, electrochemical device, electric automobile and electronic product
CN112687839A (en) * 2020-12-24 2021-04-20 惠州亿纬锂能股份有限公司 Pole piece, preparation method thereof and lithium ion battery
WO2022074498A1 (en) * 2020-10-08 2022-04-14 Indian Space Research Organisation Lithium supercapattery with stacked or wound negative and positive electrodes sets along with separator
CN114524432A (en) * 2022-02-09 2022-05-24 蜂巢能源科技股份有限公司 Lithium ion battery cathode material, preparation method thereof and lithium ion battery

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002198034A (en) * 2000-12-26 2002-07-12 Shin Kobe Electric Mach Co Ltd Nonaqueous electrolyte secondary cell
CN101373826A (en) * 2007-08-24 2009-02-25 比亚迪股份有限公司 Silicium cathode and lithium ion secondary battery containing the same, and method for preparing the same
CN104916809A (en) * 2014-03-12 2015-09-16 中国科学院金属研究所 Integrated flexible electrode
JP2019153404A (en) * 2018-03-01 2019-09-12 国立研究開発法人物質・材料研究機構 Negative electrode for secondary battery, manufacturing method thereof, and secondary battery using the same
JP2020009916A (en) * 2018-07-09 2020-01-16 サン電子工業株式会社 Electrolytic capacitor and electronic apparatus using the same
CN109755557A (en) * 2019-01-04 2019-05-14 桑顿新能源科技有限公司 A kind of safe high-voltage high-energy-density lithium ion battery and preparation method thereof
CN112349910A (en) * 2019-04-28 2021-02-09 宁德时代新能源科技股份有限公司 Negative current collector, negative pole piece, electrochemical device, electric automobile and electronic product
CN110943215A (en) * 2019-05-31 2020-03-31 宁德时代新能源科技股份有限公司 Lithium ion secondary battery
CN110556511A (en) * 2019-09-03 2019-12-10 珠海格力电器股份有限公司 Lithium battery negative pole piece with excellent cycle performance, preparation method thereof and lithium ion battery
CN112103471A (en) * 2020-09-08 2020-12-18 东莞维科电池有限公司 Pole piece and lithium ion battery
WO2022074498A1 (en) * 2020-10-08 2022-04-14 Indian Space Research Organisation Lithium supercapattery with stacked or wound negative and positive electrodes sets along with separator
CN112687839A (en) * 2020-12-24 2021-04-20 惠州亿纬锂能股份有限公司 Pole piece, preparation method thereof and lithium ion battery
CN114524432A (en) * 2022-02-09 2022-05-24 蜂巢能源科技股份有限公司 Lithium ion battery cathode material, preparation method thereof and lithium ion battery

Also Published As

Publication number Publication date
CN115566137B (en) 2023-05-26

Similar Documents

Publication Publication Date Title
CN111276690B (en) Low-porosity positive pole piece, preparation method thereof and application of positive pole piece in solid-state lithium metal battery
CN108807974B (en) Lithium ion battery
CN113097441B (en) Electrochemical device and electronic device
KR102502618B1 (en) Secondary battery, battery module including secondary battery, battery pack and device
WO2021184262A1 (en) Lithium-ion battery cell, preparation method for same, and lithium-ion battery having same
CN111785925B (en) Pole piece and application thereof, and low-temperature-rise high-safety lithium ion battery containing same
WO2011103708A1 (en) Capacitor cell with high-specific-energy organic system
WO2015018114A1 (en) Aqueous composite binder of natural polymer derivative-conducting polymer and application thereof
CN105470576A (en) High voltage lithium battery cell and preparation method therefor, and lithium ion battery
CN113594408B (en) Negative plate and battery
CN101867061A (en) Lithium-ion battery with long service life and high power and preparation method thereof
CN212907803U (en) Lithium ion battery with high-rate charge and discharge
CN112909220A (en) Secondary battery and device containing the same
JP7282925B2 (en) Positive electrode for lithium secondary battery, manufacturing method thereof, and lithium secondary battery including the same
CN111029566A (en) Quick-charging flexible-package lithium ion battery
CN102694176A (en) Electrode for non-aqueous electrolyte battery, and non-aqueous electrolyte battery using the electrode
CN111786040A (en) Pole piece, application thereof and low-temperature-rise long-life lithium ion battery containing pole piece
US10541453B2 (en) Battery module for starting a power equipment
CN105761944A (en) Composite positive plate for hybrid super capacitor and preparation method thereof, and hybrid super capacitor
JP2019175657A (en) Lithium ion secondary battery
WO2022001634A1 (en) Laminated composite battery having three lugs
CN116825962A (en) Sodium ion battery composite negative electrode, battery and preparation method of negative electrode
JP2012009284A (en) Lithium-ion secondary battery
CN115566137B (en) High-energy-density pole piece, preparation method thereof and battery cell
CN212365998U (en) Electrode structure of lithium solid-state battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant