CN112151873A - Current collector-free battery core, preparation method thereof and lithium ion battery - Google Patents

Current collector-free battery core, preparation method thereof and lithium ion battery Download PDF

Info

Publication number
CN112151873A
CN112151873A CN202011125829.6A CN202011125829A CN112151873A CN 112151873 A CN112151873 A CN 112151873A CN 202011125829 A CN202011125829 A CN 202011125829A CN 112151873 A CN112151873 A CN 112151873A
Authority
CN
China
Prior art keywords
material layer
electrode material
negative electrode
positive electrode
separator
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.)
Pending
Application number
CN202011125829.6A
Other languages
Chinese (zh)
Inventor
徐洲
李涛
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.)
Shenzhen Poly Lithium Energy Co ltd
Original Assignee
Shenzhen Poly Lithium 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 Shenzhen Poly Lithium Energy Co ltd filed Critical Shenzhen Poly Lithium Energy Co ltd
Priority to CN202011125829.6A priority Critical patent/CN112151873A/en
Publication of CN112151873A publication Critical patent/CN112151873A/en
Pending legal-status Critical Current

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
    • 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
    • H01M10/05—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
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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

Landscapes

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

Abstract

The invention discloses a current collector-free battery core, a preparation method thereof and a lithium ion battery. The battery cell comprises at least 1 battery cell unit, wherein the battery cell unit comprises a positive electrode material layer, a negative electrode material layer and an isolation structure filled between the positive electrode material layer and the negative electrode material layer, and the isolation structure is respectively in contact with the positive electrode material layer and the negative electrode material layer. The battery core provided by the invention has the advantages that the current collector is not arranged, the energy density of the battery is improved, and the safety performance of the battery core in the production and use processes is ensured.

Description

Current collector-free battery core, preparation method thereof and lithium ion battery
Technical Field
The invention belongs to the technical field of energy storage, and relates to a current collector-free battery core, a preparation method thereof and a lithium ion battery.
Background
In recent years, with the development of economy and the advancement of technology, energy problems and environmental problems have become important concerns of all people at present. The excessive consumption of fossil fuels and the growing demand for energy have made the development and utilization of clean energy extremely urgent.
The lithium ion secondary battery is used as a preferred power supply in the fields of digital products, electric automobile products and the like at present because of the advantages of high energy density, high working voltage, long cycle life, no pollution and the like. With the increasing popularity of portable intelligent devices, development of light and thin battery cells with portability, small size, high energy density and high safety has recently become a common research hotspot in academic and industrial circles. How to make portable intelligent equipment really meet the daily life needs of people, how to make intelligent equipment have not only less volume but also long-time endurance, it becomes one of the technical difficulties that the development of battery electric core corresponding to it is urgent to overcome.
CN109888168A discloses a positive electrode, a preparation method thereof and a battery with the positive electrode, wherein the positive electrode is a carbon fiber network structure loaded by a positive electrode material and nano titanium dioxide, and the preparation method of the positive electrode is as follows: soaking the paper in titanate solution, taking out and drying to obtain a composite paper, ultrasonically dispersing a positive electrode material and deionized water according to a certain proportion to obtain a dispersion liquid with a certain solubility, then mixing the composite paper with the dispersion liquid to perform hydrolysis reaction, taking out and drying to obtain a titanium dioxide and positive electrode material loaded complex; and then carrying out high-temperature heating treatment on the complex in the protective gas atmosphere to obtain a structure of loading nano titanium dioxide and a positive electrode material on a carbon fiber network, namely a positive electrode and a battery with the positive electrode. The technical scheme is used for preparing the self-supporting flexible anode without a bonding agent and a current collector, and can simplify the electrode preparation process, reduce the working procedures, reduce the cost, improve the energy density, and improve the conductivity and the safety. However, the invention requires that the electrode is prepared first and then assembled into the battery, the process is relatively complicated, and the electrode structure is not compact enough.
CN108807958A discloses a tin dioxide-graphene-carbon nanotube flexible negative electrode material, a preparation method and an application thereof, wherein the preparation method comprises: dissolving tin salt in pure water, heating to 90-230 ℃, preserving heat for 3-72 hours, cooling to room temperature, adding saccharides, stirring for dissolving, heating to 90-230 ℃, preserving heat for 1-72 hours, adding graphene oxide dispersion liquid, stirring and mixing uniformly, adding short single-walled carbon nanotubes, styrene-butadiene rubber and hydroiodic acid solution, stirring uniformly, performing ultrasonic treatment, performing reduced pressure filtration on the mixed solution to obtain a composite membrane, and drying to obtain the composite membrane. The preparation method of the flexible negative electrode material is simple, environment-friendly and low in cost, and the problem of volume expansion of tin dioxide is relieved by the structure of the three-dimensional carbon skeleton; the addition of SBR improves the mechanical property of the membrane so that the membrane can be directly used as a flexible electrode material under the condition of no current collector and no binder; the prepared composite membrane material has excellent cycle performance, high energy density, high rate performance and long service life. However, the preparation process of the flexible negative electrode is complex, and the tightness of the assembled battery is not good enough.
Aiming at the development trend of the lithium ion battery cell, at present, no mature technology and process are available in the industry to prepare products meeting the requirements, most devices only stay in the research stage, and the problems that the performance cannot meet the requirements, the energy density is low, the preparation cost is high, the preparation process is complex and the like need to be solved are really applied.
In summary, it is an urgent need to develop a method for ensuring the energy density of the battery cell, ensuring the safety performance of the battery cell during the production and use processes, and having a simple preparation process.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a current collector-free battery cell, a method for manufacturing the same, and a lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a current collector-free battery core, which includes at least one battery core unit, where the battery core unit includes a positive electrode material layer, a negative electrode material layer, and an isolation structure filled between the positive electrode material layer and the negative electrode material layer, and the isolation structure is in contact with the positive electrode material layer and the negative electrode material layer, respectively.
The number of the cell units in the invention is at least 1, for example, 1, 2, 3, 5, 6, 8, 10, 12 or 15.
In the battery core provided by the invention, the isolation structure effectively isolates the positive electrode and the negative electrode, the energy density of the battery is improved because of no current collector, and the safety performance of the battery core in the production and use processes is ensured because of the compact electrode structure.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
Preferably, the cell units are of a laminated structure, and the laminated structure refers to: a structure formed by stacking layers upon one another.
Preferably, the number of the units is at least 2, and the vertical section of the isolation structure is zigzag, wherein two parallel sides of the zigzag are respectively located at the edge of the anode material layer and the edge of the cathode material layer.
Preferably, the included angle of the zigzag is 90 ℃.
Preferably, in the vertical cross section, the thickness of the portion of the separator structure located between the positive electrode material layer and the negative electrode material layer is 10 μm to 300 μm, such as 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 85 μm, 100 μm, 150 μm, 200 μm, 240 μm, 265 μm, 300 μm, etc., preferably 20 μm to 200 μm.
Preferably, the thickness of the separator structure at the edge portions of the positive electrode material layer/negative electrode material layer is independently 100 μm to 1000 μm, such as 100 μm, 150 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 650 μm, 750 μm, 800 μm, 900 μm, 1000 μm, or the like, preferably 200 μm to 500 μm.
In the battery core, the isolation structure can be integrated or partitioned, the isolation structure can be made of a single type or multiple types, and the insulation material commonly used in the field can be used for the invention as long as the effect of isolating the positive electrode and the negative electrode can be achieved.
For example, the material of the portion of the isolation structure located between the positive electrode material layer and the negative electrode material layer may be the same as or different from the material of the portion of the isolation structure located at the edge of the positive electrode material layer/the negative electrode material layer, and in terms of the preparation method, the isolation structure may be prepared at one time (e.g., one filling molding) or may be prepared multiple times (e.g., two filling molding).
The specific types of the positive electrode material layer and the negative electrode material layer are not limited in the present invention, and the positive electrode material layer and the negative electrode material layer which are commonly used in the art and can achieve the same effect can be used in the present invention.
Preferably, the positive electrode material layer includes a positive electrode active material including, but not limited to, at least one of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium manganese phosphate, ternary nickel-cobalt-manganese material, and ternary nickel-cobalt-aluminum material, a binder, and a conductive agent.
Preferably, the negative electrode material layer includes a negative electrode active material including, but not limited to, at least one of lithium titanate, natural graphite, artificial graphite, carbon fiber, soft carbon, hard carbon, mesocarbon microbeads, elemental silicon, silicon oxy compound, and silicon-carbon composite, a binder, and optionally a conductive agent. The "optional conductive agent" means: the negative electrode material layer may or may not contain a conductive agent, for example, when other components in the negative electrode material layer satisfy that the negative electrode material layer has good conductivity, no additional conductive agent is needed.
The positive electrode material layer and/or the negative electrode material layer of the invention may further include other additives suitable for preparing the positive electrode material layer and/or the negative electrode material layer, such as a surfactant or a pore-forming agent.
Preferably, the binder in the positive electrode material layer and the negative electrode material layer is independently selected from at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid and polyvinyl alcohol, such as polyvinylidene fluoride, polytetrafluoroethylene, a combination of polyvinylidene fluoride and polyacrylic acid, a combination of polyvinylidene fluoride, polytetrafluoroethylene and polyvinyl alcohol, and the like. However, the above-mentioned binder is not limited thereto, and other binders commonly used in the art to achieve the same effect may be used in the present invention.
Preferably, the conductive agent in the positive electrode material layer and the negative electrode material layer is independently selected from at least one of conductive carbon black, acetylene black, ketjen black, Super P, Super S, carbon nanotube, graphene, porous carbon and carbon fiber, such as conductive carbon black, ketjen black, a combination of acetylene black and Super P, a combination of Super P, carbon nanotube and porous carbon, and the like, but is not limited to the above listed conductive agents, and other conductive agents commonly used in the art to achieve the same effect may also be used in the present invention.
In the invention, at least the part of the isolation structure, which is positioned between the anode material layer and the cathode material layer, has lithium ion conductivity, so that the transmission of lithium ions between the anode and the cathode is ensured.
In the invention, the materials of the isolation structures can be completely the same or different as a whole, the materials are not particularly limited, and the effects of isolating the positive electrode and the negative electrode to avoid short circuit and ensuring that lithium ions can be transmitted between the positive electrode and the negative electrode can be achieved. The material of the isolation structure includes, but is not limited to, at least one of a solid electrolyte, a ceramic dielectric material, and a polyolefin.
Preferably, at least a portion of the separator structure located between the positive electrode material layer and the negative electrode material layer has pores.
In order to obtain better effects of isolating the positive electrode and the negative electrode and transmitting lithium ions, the following preferred scheme can be adopted:
solid electrolytes such as oxide solid electrolytes, sulfide solid electrolytes or polymer solid electrolytes, more specifically, LLZO, LLZTO and the like, are directly used as a separator material for producing a separator structure, and the actual production may be performed by pressure coating using a dry powder, a granular dry material, a granular wet material of a solid electrolyte, such as spray coating or 3D printing.
② the isolation structure is prepared by adopting a porous polyolefin layer, such as a porous PP layer or a porous PE layer, and the actual preparation can adopt a fitting mode.
Thirdly, ceramic dielectric material is used as isolation material for preparing the isolation structure, and the ceramic dielectric material, adhesive and solvent are mixed and then pressure coating, such as spraying or 3D printing, is adopted for practical preparation.
(iv) mixing the polyolefin in molten or powdered form with a pore-forming agent, including but not limited to volatile solvents or metal oxide particles (e.g., Al)2O3、TiO2、SiO2、MgO、CaO, etc.), wherein the metal particles increase stacking holes to provide a transport channel for lithium ions, and have good thermal stability to improve the safety of the battery.
Preferably, the battery core is further provided with a positive electrode tab and a negative electrode tab.
For the technical scheme that the number of the battery cell units is 1, the form of the isolation structure is not limited, the isolation structure can be an isolation layer positioned between a positive electrode material layer and a negative electrode material layer, or can comprise an isolation layer positioned between the positive electrode material layer and the negative electrode material layer and isolation parts (the vertical sections of the isolation parts are Z-shaped) positioned at the edges of the positive electrode material layer and the negative electrode material layer, and the positive electrode tab and the negative electrode tab can be in contact with the positive electrode material layer and the negative electrode material layer respectively as long as the positive electrode tab and the negative electrode.
For the technical scheme that the number of electric core unit is 2 at least, isolation structure both including the isolation layer that is located between the two and including the isolation part (its vertical cross section is the zigzag) that is located anodal material layer and negative material layer edge, the setting of anodal ear and negative pole ear needs to satisfy: and the two edges with the isolation parts are respectively provided with a conductive layer for connecting at least two positive electrode material layers and using the positive electrode material layers for positive electrode lug connection, and at least two negative electrode material layers and using the negative electrode material layers for negative electrode lug connection.
In a second aspect, the present invention provides a method for preparing a current collector-free cell according to the first aspect, the method comprising the steps of:
(1) respectively preparing a first mixture containing a positive electrode active material, a binder and a conductive agent, and a second mixture containing a negative electrode active material, a binder and an optional conductive agent;
(2) preparing a positive material layer and a negative material layer by respectively adopting the first mixture and the second mixture, preparing an isolation structure of an integrated structure or a separation structure by adopting an isolation material, and attaching the positive material layer, the negative material layer and the isolation structure to enable the isolation structure to be filled between the positive material layer and the negative material layer to obtain the current collector-free battery core.
The present invention provides a method for preparing a current collector-free cell according to the first aspect, comprising the steps of:
(1') separately preparing a first mix containing a positive electrode active material, a binder and a conductive agent, and a second mix containing a negative electrode active material, a binder and optionally a conductive agent;
(2') coating any one of the first mixture and the second mixture on the substrate table to form a first polar material layer, wherein the first polar material layer is a positive electrode material layer or a negative electrode material layer;
(3') filling and/or coating a material containing a spacer substance on a surface of the first polar material layer on the substrate table to form a spacer material layer;
and (4 ') filling and/or coating a mixture with the polarity opposite to that of the mixture adopted in the step (2') on the surface of the isolating material layer to form a second polarity material layer, and filling the isolating material layer between the positive electrode material layer and the negative electrode material layer to obtain the battery core without the current collector.
The preferred technical scheme adopts a laminated process, a plurality of battery cell units can be obtained at one time, the working efficiency is improved, the shape and the size of the battery cell are controllable, and the prepared lithium ion battery has good safety.
The positive and negative electrodes and the interlayer material are prepared and formed at one time, the structure is compact, and the energy density and the safety are higher.
As a preferable embodiment of the method according to the present invention, the method further comprises the steps of (3 ') filling and/or coating a material containing a separator on the outer side of at least one side edge of the first polar material layer to form a first separator, and (4 ') filling and/or coating a material containing a separator on the surface of the separator to form a second separator, wherein the first separator, the second separator and the separator are connected to form a separator structure having a zigzag vertical cross-section, and the step (4 ') is followed by at least 1 step (3 ') and (4 ') in sequence to form at least 2 cell units and the zigzag separator structure.
In the present invention, the forms of the first mixture and the second mixture are not limited, as long as the first polar material layer and the second polar material layer can be formed tightly by combining with a certain process, and the first polar material layer and the second polar material layer may be, for example, dry powder, dry particle, wet particle, slurry, or the like.
Preferably, the coating in step (2 ') and step (4') is pressure coating, and the pressure coating means that the coating method fixes the raw material to the surface to be coated under the action of a certain pressure, including but not limited to at least one of 3D printing and spraying.
Preferably, the filling manner in step (4') may be deposition. Preferably, the coating of step (3') is carried out by casting.
In the method, the cell product with the preset layer number and shape can be directly prepared, or the cell product can be obtained by preparing the cell with the preset layer number at half cost and cutting. The cutting mode includes but is not limited to laser cutting, linear cutting and cutter cutting.
The manufacturing process is simple to operate, the shape and the size of the battery cell are controllable, and meanwhile, the safety performance of the battery cell in the production and use processes can be guaranteed.
In a third aspect, the present invention provides a lithium ion battery, which includes the current collector-free battery cell of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a laminated current collector-free lithium ion battery cell, which has higher energy density due to the absence of a current collector.
2. The cell structure is innovatively constructed through a laminated manufacturing process. Not only simplifies the manufacturing process, but also can effectively improve the energy density of the battery.
3. The lithium ion battery core manufactured by the invention has the characteristic of good safety due to the compact electrode structure.
4. According to the cell manufacturing process, a plurality of units can be obtained by one-time manufacturing, and the working efficiency is improved.
5. The shape, size and capacity of the battery cell are controllable, and the battery cell is easy to realize commercial application.
Drawings
FIG. 1 is a schematic view of a positive electrode material layer region and a peripheral blank region according to a first embodiment;
FIG. 2 is a schematic view of a region of the negative electrode material layer and a peripheral blank region according to the first embodiment;
fig. 3 is a schematic cross-sectional view of a laminated cell unit according to the first embodiment;
FIG. 4 is a schematic view of a layer region and a peripheral blank region of the cathode material in the second embodiment;
fig. 5 is a schematic view of the negative electrode material layer region and the peripheral blank region in the second embodiment.
Detailed Description
The technical solutions of the present invention are further described by the following embodiments with reference to the accompanying drawings, but the present invention is not limited thereto.
The present invention will be described in detail by way of examples. The embodiments described below with reference to the drawings are exemplary and intended to be illustrative of the present invention and should not be construed as limiting the scope of the present invention. The specific process parameters and the like of the following examples are also only one example of suitable ranges, and a person skilled in the art can select the process parameters and the like within the suitable ranges through the description of the invention, and the specific selection of the following examples is not limited.
First, a basic scheme of materials used in the examples of the present invention is briefly described:
the invention provides a laminated current collector-free lithium ion battery cell and a manufacturing process thereof, wherein the manufacturing process of the cell comprises the following raw materials of a positive electrode material layer: selecting a positive electrode active material, a conductive agent and a binder to mix and prepare a dry powder material; raw materials of the anode material layer: selecting a negative electrode active material and a binder to mix to prepare a dry powder; isolating substance: at least one of a ceramic dielectric material, a solid electrolyte material and a polyolefin is selected. The method comprises the following steps:
selecting a positive electrode active material lithium cobaltate, a conductive agent acetylene black and a binder polyvinylidene fluoride to mix to prepare a dry powder, and spraying the dry powder on a designated area of a hydrophobic easily-stripped platform to obtain a positive electrode material layer, wherein the specific area is shown in figure 1 and comprises a positive electrode material layer area 111 and a peripheral blank area 112;
spraying an isolating material above the positive electrode material layer and in the blank area on the periphery, specifically, mixing a ceramic dielectric material with a binder and a solvent to prepare slurry, and spraying to obtain a plane full of the isolating material again;
thirdly, spraying a negative electrode material layer in a specified area above the plane of the step, wherein the specific area is as shown in fig. 2 and comprises a negative electrode material layer area 113 and a peripheral blank area 114, and the area is consistent with the area of the positive electrode material layer in shape and size, and most importantly, the two material layers must be staggered;
step four, spraying and filling the blank area 114 with an isolating substance material;
and fifthly, drying, cutting and peeling the prepared laminated material layer integrally to obtain the laminated current collector-free lithium ion battery cell.
Note that, the cutting process adopts a laser cutting machine, and the laminated material layer can be firstly cut into an integral strip shape, and then cut into bare cells with different shapes and sizes according to actual needs. The section of the bare cell unit after cutting is as shown in fig. 3, and the whole unit 1, the unit of this embodiment, includes a positive electrode material layer 11, a negative electrode material layer 12 and a separator material layer 13.
A plurality of units can be obtained by one-time manufacturing, and the working efficiency is improved.
The shape, the size and the capacity of the cell unit can be controlled.
The embodiment of the invention also provides a lithium ion battery, in particular to a laminated current collector-free lithium ion battery, which is prepared by adopting the prepared naked battery cell, and the specific implementation mode is as follows:
firstly, coating a layer of silver paste or other conductive substances on the cut electrode end surface of a cell unit comprising a positive electrode material layer, a negative electrode material layer and a separation material layer;
then, soaking the battery core with electrolyte to fill the battery core isolating substance material layer with the electrolyte;
then, assembling the battery cell filled with the electrolyte with a shell with a corresponding size to obtain a lithium ion battery; or, the battery core is packaged by using an insulating coating or a coating layer, and the tab is led out to obtain the lithium ion battery.
Example one
Selecting a positive electrode active material lithium cobaltate, a conductive agent acetylene black and a binder polyvinylidene fluoride to mix to prepare a dry powder, and spraying the dry powder on a designated area of a hydrophobic easily-stripped platform to obtain a positive electrode material layer with the thickness of 150 mu m and the surface density of 400g/m2Specific areas are shown in fig. 1, and include a positive electrode material layer area 111 and a peripheral blank area 112;
spraying an isolating material above the positive electrode material layer and in the blank area at the periphery, specifically, spraying a ceramic dielectric material Al2O3Mixing with a binder polyvinylidene fluoride and a solvent N-methyl pyrrolidone to prepare slurry, and spraying to obtain a plane full of the isolation material with the thickness of 30 mu m;
thirdly, spraying a negative electrode material layer in a specified area above the plane in the step, wherein the thickness of the negative electrode material layer is 150 mu m, and the area density of the negative electrode material layer is 200g/m2Specific regions include a negative electrode material layer region 113 and a peripheral blank region 114, as shown in fig. 2, and it is noted that the regions are in accordance with the shape and size of the regions of the positive electrode material layer, and the regions are shifted by 2mm in the horizontal direction compared with the regions of the positive electrode material layer;
step four, spraying and filling the blank area 114 with the thickness of 150 μm by using an isolating substance material;
and fifthly, drying, cutting and peeling the prepared laminated material layer integrally to obtain the laminated current collector-free lithium ion battery cell.
Note that, the cutting process adopts a laser cutting machine, linear cutting or cutter cutting, and the laminated material layer can be firstly cut into an integral strip shape, and then cut into bare cells with different shapes and sizes according to actual needs. The section of the bare cell unit after cutting is as shown in fig. 3, and the whole unit 1, the unit of this embodiment, includes a positive electrode material layer 11, a negative electrode material layer 12 and a separator material layer 13.
A plurality of units can be obtained by one-time manufacturing, and the working efficiency is improved.
The shape, the size and the capacity of the cell unit can be controlled.
Example two
The invention relates to a laminated current collector-free lithium ion battery cell and a manufacturing process thereof, wherein the manufacturing process of the cell basically has the same steps as the first embodiment, only the difference of specific areas is included, and the specific steps are as follows:
step one, spraying a positive electrode material layer on a designated area of a hydrophobic easily-stripped platform, wherein the specific area is shown in fig. 4 and comprises a positive electrode material layer area 211 and a peripheral blank area 212;
secondly, spraying an isolating substance material above the anode material layer and in the blank area on the periphery of the anode material layer to obtain a plane full of the isolating material again;
step three, spraying a negative electrode material layer in a specified area above the plane of the step, wherein the specific area is as shown in fig. 5 and comprises a negative electrode material layer area 213 and a peripheral blank area 214, and the area is in accordance with the area of the positive electrode material layer in shape and size and is displaced by 2mm in the horizontal direction compared with the area of the positive electrode material layer;
step four, spraying and filling the blank area 214 with an isolating substance material;
and fifthly, drying, cutting and peeling the prepared laminated material layer integrally to obtain the laminated current collector-free lithium ion battery cell.
A plurality of units can be obtained by one-time manufacturing, and the working efficiency is improved.
The shape and the size of the battery cell unit can be controlled when the material layer is sprayed.
In this embodiment, the thickness and the areal density of the positive electrode material layer and the negative electrode material layer are the same as those in the first embodiment.
EXAMPLE III
The laminated current collector-free lithium ion battery of the embodiment is manufactured by the bare cell prepared in the first embodiment and the bare cell prepared in the second embodiment, and the specific implementation manner is as follows:
firstly, coating a layer of silver paste on the end face of a cut electrode of the cell unit containing the positive electrode material layer, the negative electrode material layer and the isolating substance material layer obtained in the first embodiment and the second embodiment;
then, soaking the battery core with electrolyte to fill the battery core isolating substance material layer with the electrolyte;
and then assembling the battery cell filled with the electrolyte with a shell with a corresponding size to obtain the lithium ion battery.
In this embodiment, the thickness and the areal density of the positive electrode material layer and the negative electrode material layer are the same as those in the first embodiment.
Example four
The laminated current collector-free lithium ion battery of the embodiment is manufactured by the bare cell prepared in the first embodiment and the bare cell prepared in the second embodiment, and the specific implementation manner is as follows:
firstly, coating a layer of silver paste on the end face of a cut electrode of the cell unit containing the positive electrode material layer, the negative electrode material layer and the isolating substance material layer obtained in the first embodiment and the second embodiment;
then, soaking the battery core with electrolyte to fill the battery core isolating substance material layer with the electrolyte;
and then, packaging the battery cell by using an insulating coating or a coating layer, and leading out a tab to obtain the lithium ion battery.
In this embodiment, the thickness and the areal density of the positive electrode material layer and the negative electrode material layer are the same as those in the first embodiment.
EXAMPLE five
Selecting a positive electrode active material lithium cobaltate, a conductive agent acetylene black, a binder polyvinylidene fluoride and a solvent N-methyl pyrrolidone, mixing to prepare slurry, and 3D printing the slurry on a specified area of a hydrophobic easily-stripped platform to obtain a positive electrode material layer with the thickness of 150 mu m and the surface density of 400g/m2Drying and shaping;
coating isolation material above the positive electrode material layer and in the peripheral blank area, specifically, coating ceramic dielectric material Al2O3Is polymerized with a binderMixing vinyl fluoride and solvent N-methyl pyrrolidone to prepare slurry, performing 3D printing to obtain a plane full of the isolation material with the thickness of 30 mu m, and drying and shaping;
step three, coating a negative electrode material layer in a specified area above the plane of the step, wherein the thickness of the negative electrode material layer is 150 mu m, and the area density of the negative electrode material layer is 200g/m2The region is displaced by 2mm in the horizontal direction compared with the region of the positive electrode material layer;
filling the blank area with an isolating substance material, wherein the thickness of the blank area is 150 mu m;
and fifthly, drying, cutting and peeling the prepared laminated material layer integrally to obtain the laminated current collector-free lithium ion battery cell.
The cutting process of the embodiment adopts laser cutting.
A plurality of units can be obtained by one-time manufacturing, and the working efficiency is improved.
The shape, the size and the capacity of the cell unit can be controlled.
EXAMPLE six
Selecting a positive electrode active material lithium cobaltate, a conductive agent acetylene black and a binder polyvinylidene fluoride to mix to prepare a dry powder, and spraying the dry powder on a designated area of a hydrophobic easily-stripped platform to obtain a positive electrode material layer with the thickness of 150 mu m and the surface density of 400g/m2，；
Spraying an isolating material above the positive electrode material layer and in the blank area at the periphery, specifically, spraying a ceramic dielectric material Al2O3Mixing with a binder polyvinylidene fluoride and a solvent N-methyl pyrrolidone to prepare slurry, and spraying to obtain a plane full of the isolation material with the thickness of 40 mu m;
thirdly, spraying a negative electrode material layer in a specified area above the plane in the step, wherein the thickness of the negative electrode material layer is 150 mu m, and the area density of the negative electrode material layer is 200g/m2The region is displaced by 2mm in the horizontal direction compared with the region of the positive electrode material layer;
step four, spraying and filling the blank area with the thickness of 150 mu m by using an isolating substance material;
and fifthly, drying, cutting and peeling the prepared laminated material layer integrally to obtain the laminated current collector-free lithium ion battery cell.
A plurality of units can be obtained by one-time manufacturing, and the working efficiency is improved.
The shape, the size and the capacity of the cell unit can be controlled.
EXAMPLE seven
Selecting a positive active material lithium manganate, a conductive agent acetylene black and a binder polyvinylidene fluoride to mix to prepare a dry powder, and spraying the dry powder on a designated area of a hydrophobic easily-stripped platform to obtain a positive material layer with the thickness of 150 mu m and the surface density of 400g/m2；
Secondly, spraying an isolating substance material above the anode material layer and in a peripheral blank area, specifically, directly spraying a solid electrolyte to obtain a plane full of the isolating material, wherein the thickness of the plane is 30 microns;
thirdly, spraying a negative electrode material layer in a specified area above the plane in the step, wherein the thickness of the negative electrode material layer is 150 mu m, and the area density of the negative electrode material layer is 200g/m2The region is displaced by 2mm in the horizontal direction compared with the region of the positive electrode material layer;
step four, spraying and filling the blank area with the thickness of 150 mu m by using an isolating substance material;
and fifthly, drying, cutting and peeling the prepared laminated material layer integrally to obtain the laminated current collector-free lithium ion battery cell.
A plurality of units can be obtained by one-time manufacturing, and the working efficiency is improved.
The shape, the size and the capacity of the cell unit can be controlled.
Comparative example 1
Selecting a positive electrode active material lithium cobaltate, a conductive agent acetylene black and a binder polyvinylidene fluoride to mix to prepare a dry powder, and spraying the dry powder on a designated area of a hydrophobic easily-stripped platform to obtain a positive electrode material layer with the thickness of 150 microns;
step two, the anode material layer is covered withAnd spraying isolation material on the peripheral blank region, specifically, using ceramic dielectric material Al2O3Mixing with a binder polyvinylidene fluoride and a solvent N-methyl pyrrolidone to prepare slurry, and spraying to obtain a plane full of the isolation material with the thickness of 30 mu m;
thirdly, spraying a negative electrode material layer with the thickness of 150 μm in a specified area above the plane of the step, and noting that the area completely corresponds to the area of the positive electrode material layer without dislocation;
step four, spraying and filling the blank area with the thickness of 150 mu m by using an isolating substance material;
and fifthly, drying, cutting and peeling the prepared laminated material layer integrally to obtain the laminated current collector-free lithium ion battery cell.
The battery core prepared by the embodiment has defects in structure, and cannot lead out a tab and form a lithium ion battery.
Comparative example No. two
And preparing positive electrode slurry by adopting the positive electrode active material, the conductive agent and the binder with the same type and content as those in the first embodiment, coating the positive electrode slurry on the surface of the aluminum foil, and drying to obtain the positive electrode piece.
And preparing negative electrode slurry, coating the negative electrode slurry on the surface of the copper foil, and drying to obtain a negative electrode plate, wherein the composition of a negative electrode material layer in the negative electrode plate is the same as that in the first embodiment.
And (3) adopting a positive pole piece and a negative pole piece, isolating the positive pole piece and the negative pole piece by using a diaphragm, and laminating to obtain the battery core.
And (3) effect analysis:
firstly, the energy density is high, and the electrochemical performance is good:
in the existing typical cell structure, as in comparative example two, the ratio of the weight occupied by the copper foil and the aluminum foil to the positive and negative active materials is about 1:5 (about 1:8 for positive electrode and about 1:2 for negative electrode). While copper foil and aluminum foil do not contribute energy.
In the embodiment of the application, no copper foil or aluminum foil exists, and under the condition of the same ratio of the conductive agent to the binder, the weight of the battery cell is reduced, and the energy density of the battery cell is improved.
Even if the proportion of the conductive agent and the adhesive is increased, the capacity and the energy density of the battery cell can be improved under the condition that the increasing proportion is lower than the specific gravity of copper foil and aluminum foil in the existing battery cell structure (for example, the increasing proportion is not more than 5 percent), the weight of the battery cell can be reduced by about 15 percent, and the energy density is converted into the energy density, namely the energy density is increased by about 15 percent.
Secondly, the safety is good:
compared with the existing battery cell structure, the diaphragm made of the traditional PP/PE material is cancelled, and after the diaphragm is replaced by the inorganic oxide material, the diaphragm does not shrink and burn at high temperature, so that the safety guarantee is improved.
The foregoing is merely an exemplary embodiment of the invention and other variations may be readily made without departing from the true scope of the invention as described in the following claims.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The utility model provides a no electric core of mass flow body, its characterized in that, electric core includes 1 at least electric core unit, electric core unit includes anodal material layer, negative pole material layer and packs and be in anodal material layer and the isolation structure between the negative pole material layer, isolation structure contacts with anodal material layer and negative pole material layer respectively.
2. The currentless cell of claim 1, wherein the cell unit is a laminate structure;
preferably, the number of the battery cell units is at least 2, and the vertical section of the isolation structure is zigzag, wherein two parallel edges of the zigzag are respectively located at the edge of the positive electrode material layer and the edge of the negative electrode material layer;
preferably, the included angle of the zigzag is 90 ℃.
3. The currentless cell of claim 2, wherein, in the vertical cross-section, the thickness of the portion of the separator structure between the positive electrode material layer and the negative electrode material layer is 10 μ ι η to 300 μ ι η, preferably 20 μ ι η to 200 μ ι η;
preferably, the thickness of the portions of the separator structure located at the edges of the positive electrode material layer/negative electrode material layer is independently 100 μm to 1000 μm, preferably 200 μm to 500 μm.
4. The currentless cell of any of claims 1 to 3, wherein the positive electrode material layer comprises a positive electrode active material comprising at least one of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium manganese phosphate, ternary nickel cobalt manganese material, and ternary nickel cobalt aluminum material, a binder, and a conductive agent;
preferably, the negative electrode material layer comprises a negative electrode active material, a binder and an optional conductive agent, wherein the negative electrode active material comprises at least one of lithium titanate, natural graphite, artificial graphite, carbon fiber, soft carbon, hard carbon, mesocarbon microbeads, elemental silicon, silicon oxide compounds and silicon-carbon composites;
preferably, the binder in the positive electrode material layer and the negative electrode material layer is independently selected from at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid and polyvinyl alcohol;
preferably, the conductive agent in the positive electrode material layer and the negative electrode material layer is independently selected from at least one of conductive carbon black, acetylene black, ketjen black, Super P, Super S, carbon nanotube, graphene, porous carbon, and carbon fiber.
5. The currentless cell of any of claims 1 to 4, wherein at least a portion of the separator structure located between the layers of positive and negative electrode materials has lithium ion conductivity;
preferably, the material of the isolation structure comprises at least one of a solid electrolyte, a ceramic dielectric material and polyolefin;
preferably, at least a portion of the separator structure located between the positive electrode material layer and the negative electrode material layer has pores.
6. The currentless cell of any of claims 1 to 5, wherein the cell is further provided with a positive tab and a negative tab.
7. The method of making a current collector-less cell of any of claims 1-6, wherein the method comprises the steps of:
(1) respectively preparing a first mixture containing a positive electrode active material, a binder and a conductive agent, and a second mixture containing a negative electrode active material, a binder and an optional conductive agent;
(2) preparing a positive material layer and a negative material layer by respectively adopting the first mixture and the second mixture, preparing an isolation structure of an integrated structure or a separation structure by adopting an isolation material, and attaching the positive material layer, the negative material layer and the isolation structure to enable the isolation structure to be filled between the positive material layer and the negative material layer to obtain the current collector-free battery core.
8. The method for preparing a current collector-less cell according to any of claims 1 to 6, wherein the method comprises the steps of:
(1') separately preparing a first mix containing a positive electrode active material, a binder and a conductive agent, and a second mix containing a negative electrode active material, a binder and optionally a conductive agent;
(2') coating any one of the first mixture and the second mixture on the substrate table to form a first polar material layer, wherein the first polar material layer is a positive electrode material layer or a negative electrode material layer;
(3') filling and/or coating a material containing a spacer substance on a surface of the first polar material layer on the substrate table to form a spacer material layer;
and (4 ') filling and/or coating a mixture with the polarity opposite to that of the mixture adopted in the step (2') on the surface of the isolating material layer to form a second polarity material layer, and filling the isolating material layer between the positive electrode material layer and the negative electrode material layer to obtain the battery core without the current collector.
9. The method of claim 8, further comprising the steps of (3 ') filling and/or coating a material containing a separator substance on the outer side of at least one side edge of the first polar material layer to form a first separator, and (4 ') filling and/or coating a material containing a separator substance on the surface of the separator material layer to form a second separator, wherein the first separator and the second separator are connected with the separator material layer to form a separator structure with a zigzag vertical cross-section, and wherein the step (4 ') is followed by at least 1 step (3 ') and (4 ') in sequence to form at least 2 cell units and the zigzag separator structure.
10. A lithium-ion battery comprising the current collector-less cell of any of claims 1-6.
CN202011125829.6A 2020-10-20 2020-10-20 Current collector-free battery core, preparation method thereof and lithium ion battery Pending CN112151873A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011125829.6A CN112151873A (en) 2020-10-20 2020-10-20 Current collector-free battery core, preparation method thereof and lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011125829.6A CN112151873A (en) 2020-10-20 2020-10-20 Current collector-free battery core, preparation method thereof and lithium ion battery

Publications (1)

Publication Number Publication Date
CN112151873A true CN112151873A (en) 2020-12-29

Family

ID=73954076

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011125829.6A Pending CN112151873A (en) 2020-10-20 2020-10-20 Current collector-free battery core, preparation method thereof and lithium ion battery

Country Status (1)

Country Link
CN (1) CN112151873A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114583283A (en) * 2021-12-28 2022-06-03 上海瑞浦青创新能源有限公司 Method for manufacturing solid-state battery by using 3D printing technology

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114583283A (en) * 2021-12-28 2022-06-03 上海瑞浦青创新能源有限公司 Method for manufacturing solid-state battery by using 3D printing technology

Similar Documents

Publication Publication Date Title
CN108376783B (en) Lithium anode surface protective coating and preparation method thereof
CN103904290B (en) Aquo-lithium ion battery combination electrode and preparation method thereof, aquo-lithium ion battery
CN102394305B (en) Foamy copper oxide/copper lithium ion battery anode and preparation method thereof
CN106229447A (en) A kind of lithium ion battery
CN112151874A (en) Battery without current collector and preparation method thereof
CN104916809A (en) Integrated flexible electrode
CN112467308B (en) Diaphragm, preparation method thereof and lithium ion battery
CN102867983A (en) Nonaqueous secondary lithium battery
CN101154750A (en) High power gel polymer lithium ion power cell and method of producing the same
CN111710874B (en) Solid-state lithium battery, composite negative electrode and preparation method of composite negative electrode
US20220037636A1 (en) Lithium-manganese dioxide primary battary and preparation thereof
CN103346292B (en) A kind of composite lithium ion battery anode and its preparation method and application
CN109309191A (en) A kind of novel long-life energy storage lithium ion battery pole piece and lithium ion battery
CN113422044A (en) Lithium ion battery and preparation method thereof
CN101587952A (en) Compound lithium cobaltate cathode material, preparing method and application thereof
CN113675365A (en) Negative plate and lithium ion battery
CN105934845B (en) Electrical part
CN106450434A (en) High-voltage high-energy-density lithium ion battery
CN214848743U (en) Battery without current collector
CN109741956A (en) A kind of graphene-based high specific energy lithium-ion capacitor and preparation method thereof
CN113675480A (en) Lithium ion battery cell with sandwich structure, electric pile and preparation method thereof
CN117637988A (en) Negative electrode plate of high-energy-density battery, preparation method of negative electrode plate, battery and power utilization device
CN105304857A (en) Soft-package lithium iron phosphate battery
CN112151873A (en) Current collector-free battery core, preparation method thereof and lithium ion battery
CN202917600U (en) Aluminum-plastic packed high-power lithium ion 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