CN115810868B - Aqueous metal ion battery, preparation method thereof and power utilization device - Google Patents
Aqueous metal ion battery, preparation method thereof and power utilization device Download PDFInfo
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Abstract
本申请涉及一种水系金属离子电池，其包括隔膜，所述隔膜包括：基材；在所述基材的至少一个表面上的陶瓷涂层；以及在所述陶瓷涂层上的聚合物涂层，其中，所述聚合物涂层包含增稠剂。本申请还涉及一种制备水系金属离子电池的方法以及用电装置。
The present application relates to an aqueous metal ion battery, comprising a diaphragm, wherein the diaphragm comprises: a substrate; a ceramic coating on at least one surface of the substrate; and a polymer coating on the ceramic coating, wherein the polymer coating contains a thickener. The present application also relates to a method for preparing an aqueous metal ion battery and an electrical device.
Description
Technical Field
The application relates to the technical field of secondary batteries, in particular to a water-based metal ion battery, a preparation method thereof and an electric device.
Background
In recent years, as the application range of secondary batteries is becoming wider, secondary batteries are widely used in energy storage power systems such as hydraulic power, thermal power, wind power and solar power stations, and in various fields such as electric tools, electric bicycles, electric motorcycles, electric vehicles, military equipment, aerospace and the like.
The aqueous battery is a secondary battery using water as an electrolyte solvent. Aqueous batteries are becoming a hot spot for secondary battery research due to their high safety, environmental friendliness, high ionic conductivity, and the like. However, the cycle performance and safety performance of the existing aqueous battery need to be further improved.
Disclosure of Invention
The present application has been made in view of the above problems, and an object thereof is to provide an aqueous metal ion battery having excellent cycle performance and safety performance.
In order to achieve the above purpose, the application provides a water-based metal ion battery, a preparation method thereof and an electric device.
A first aspect of the present application provides an aqueous metal ion battery comprising a separator comprising:
A substrate;
A ceramic coating on at least one surface of the substrate, and
A polymer coating on the ceramic coating,
Wherein the polymeric coating comprises a thickener.
Therefore, the thickening agent is contained in the polymer coating of the water-based metal ion battery diaphragm, so that the viscosity of the thickening agent becomes high after water absorption, and the adhesion between the diaphragm and the positive and negative plates is enhanced, thereby solving the problem of fluffy electrode assemblies (battery cells) after cold pressing, and further improving the cycle performance and the safety performance of the water-based metal ion battery.
In any embodiment, the thickener comprises at least one of celluloses, silicates, polyurethanes, and polyacrylics.
In any embodiment, the celluloses include methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and hydroxypropylmethyl cellulose.
In any embodiment, the silicate comprises aluminum silicate and sodium silicate.
In any embodiment, the polyurethanes include hydrophobically modified ethoxylated polyurethanes and modified polymers thereof.
In any embodiment, the polyacrylic acid comprises polyacrylic acid, polymethacrylic acid, or a copolymer of acrylic acid and methacrylic acid.
In any embodiment, the thickener has a coating density of 0.0000649-0.000195mg/mm 2(0.1-0.3mg/1540.25mm2), alternatively 0.0000649-0.000130mg/mm 2(0.1-0.2mg/1540.25mm2). When the coating density of the thickener is within the range, the cycle performance and the safety performance of the aqueous metal ion battery can be further improved.
In any embodiment, the polymer coating has a coating density of 0.00039-0.00422mg/mm 2(0.6-6.5mg/1540.25mm2). When the coating density of the polymer coating is within the given range, good adhesion of the separator and the positive and negative plates can be ensured.
In any embodiment, the thickener is present in the polymer coating in an amount of 1.5% to 50% by weight. When the weight percentage of the thickener in the polymer coating is in the given range, the cycle performance and the safety performance of the water-based metal ion battery can be further improved while the function of the polymer coating is not affected.
A second aspect of the present application provides a method of preparing an aqueous metal-ion battery comprising a separator comprising:
A substrate;
A ceramic coating on at least one surface of the substrate, and
A polymer coating on the ceramic coating,
The polymeric coating comprises a thickener
The method for preparing the water-based metal ion battery comprises the following steps:
(1) Preparing a positive electrode plate;
(2) Preparing a negative electrode plate;
(3) Preparing the separator;
(4) Preparing an electrolyte;
(5) Preparing the aqueous metal ion battery;
wherein, the step (3) comprises:
(3-1) providing the substrate,
(3-2) Providing a ceramic slurry, coating the ceramic slurry on at least one surface of the substrate and drying to form the ceramic coating, and
(3-3) Providing a polymer slurry comprising a thickener, coating the polymer slurry on the ceramic coating and drying to form the polymer coating, thereby obtaining the separator.
Therefore, the method disclosed by the application comprises the thickening agent in the polymer coating of the water-based metal ion battery diaphragm in a simple manner, and can solve the problem that an electrode assembly (an electric core) is fluffy after cold pressing, so that the cycle performance and the safety performance of the water-based metal ion battery are improved.
A third aspect of the application provides an electrical device comprising the aqueous metal-ion battery of the first aspect of the application or prepared by the method of the second aspect of the application.
The electric device of the application comprises the water-based metal ion battery of the application, and thus has at least the same advantages as the water-based metal ion battery.
Drawings
Fig. 1 is a schematic view of an electrode assembly (cell) according to an embodiment of the present application.
Fig. 2 is a schematic view of an aqueous metal ion battery according to an embodiment of the present application.
Fig. 3 is an exploded view of the aqueous metal-ion battery according to the embodiment of the present application shown in fig. 2.
Fig. 4 is a schematic view of a battery module according to an embodiment of the present application.
Fig. 5 is a schematic view of a battery pack according to an embodiment of the present application.
Fig. 6 is an exploded view of the battery pack of the embodiment of the present application shown in fig. 5.
Fig. 7 is a schematic view of an electric device using an aqueous metal ion battery according to an embodiment of the present application as a power source.
Reference numerals illustrate:
1 battery pack, 2 upper case, 3 lower case, 4 battery module, 5 water system metal ion battery, 51 case, 52 electrode assembly, 53 top cover assembly
Detailed Description
Hereinafter, embodiments of the aqueous metal ion battery, the method for producing the same, and the electric device according to the present application will be specifically disclosed with reference to the accompanying drawings. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. This is to avoid that the following description becomes unnecessarily lengthy, facilitating the understanding of those skilled in the art. Furthermore, the drawings and the following description are provided for a full understanding of the present application by those skilled in the art, and are not intended to limit the subject matter recited in the claims.
The "range" disclosed herein is defined in terms of lower and upper limits, with the given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if minimum range values 1 and 2 are listed, and if maximum range values 3,4, and 5 are listed, the following ranges are all contemplated as 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In the present application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
All embodiments of the application and alternative embodiments may be combined with each other to form new solutions, unless otherwise specified.
All technical features and optional technical features of the application may be combined with each other to form new technical solutions, unless specified otherwise.
All the steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise specified. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, it is mentioned that the method may further comprise step (c), meaning that step (c) may be added to the method in any order, e.g. the method may comprise steps (a), (b) and (c), may also comprise steps (a), (c) and (b), may also comprise steps (c), (a) and (b), etc.
The terms "comprising" and "including" as used herein mean open ended or closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either condition satisfies the condition "A or B" that A is true (or present) and B is false (or absent), that A is false (or absent) and B is true (or present), or that both A and B are true (or present).
In the preparation process of the secondary battery, an electrode assembly (namely an electric core JR) consisting of a positive electrode plate, a diaphragm and a negative electrode plate is heated by a tunnel furnace after winding is completed to soften a polymer coating of the diaphragm, and then the polymer coating is transferred to a cold pressing plate for cold pressing to bond the diaphragm and the positive electrode plate together. However, in some aqueous metal ion batteries, the electric core JR is relatively thin, heat dissipation is fast when the battery is cooled after passing through a tunnel furnace, the temperature of a polymer coating on a diaphragm is fast reduced, bonding with positive and negative pole pieces is poor, and a fluffy electric core is easy to appear when cold pressing, so that the cycle performance and the safety performance of the aqueous metal ion battery are affected.
According to the application, the thickening agent is added into the polymer coating of the diaphragm, and the viscosity of the thickening agent becomes large after water absorption, so that the adhesion between the diaphragm and the positive and negative plates is improved, and the cycle performance and the safety performance of the water-based metal ion battery are further improved.
In one embodiment, the present application provides an aqueous metal ion battery comprising a separator comprising:
A substrate;
a ceramic coating on at least one surface of the substrate, and
A polymer coating on the ceramic coating,
Wherein the polymeric coating comprises a thickener.
Although the mechanism is not clear, the inventor surprisingly discovers that the thickening agent is contained in the polymer coating of the water-based metal ion battery diaphragm, so that the thickening agent can absorb water to enlarge the viscosity and strengthen the viscosity between the diaphragm and the positive and negative pole pieces, thereby solving the problem of fluffy battery cells after cold pressing and further improving the cycle performance and the safety performance of the water-based metal ion battery.
In addition, when the aqueous metal ion battery is an aqueous lithium ion battery, lithium deposition of the battery is also improved. The lithium ion battery is characterized in that when the bonding between the diaphragm and the positive and negative pole pieces is good, the gap between the positive and negative pole pieces is small, the lithium ion transmission distance is uniform and small, when the bonding is poor, the distance between the positive and negative pole pieces is uneven, the local distance is overlarge, the lithium ion transmission path is long, and lithium is easy to separate out. Therefore, the application can keep good adhesion between the diaphragm and the positive and negative pole pieces during cold pressing by containing the thickening agent in the polymer coating, thereby improving lithium precipitation, namely improving the safety performance of the water-based metal ion battery.
When the water-based metal ion battery is a water-based sodium ion battery, the thickener increases the adhesiveness between the pole piece and the diaphragm, and can ensure uniform sodium ion transmission distances at different positions, thereby preventing wrinkling.
In the present application, the aqueous metal ion battery is a battery whose electrolyte is an aqueous solution.
In some embodiments, the aqueous metal ion battery is an aqueous lithium, sodium, zinc, aluminum, or vanadium ion battery.
In some embodiments, the polymer coating is island-like.
In some embodiments, the thickener is an aqueous thickener, i.e., a thickener that can perform a thickening function in an aqueous system.
In some embodiments, the thickener comprises at least one of cellulosics, silicates, polyurethanes, and polyacrylics.
In some embodiments, the celluloses include methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and hydroxypropylmethyl cellulose.
In some embodiments, the silicate comprises aluminum silicate and sodium silicate.
In some embodiments, polyurethanes include hydrophobically modified ethoxylated polyurethanes and modified polymers thereof.
In some embodiments, the polyacrylic acid comprises polyacrylic acid, polymethacrylic acid, or a copolymer of acrylic acid and methacrylic acid.
In the present application, polyacrylic acids include salts thereof, such as sodium polyacrylate, sodium polymethacrylate, and the like.
In some embodiments, the cellulose has a number average molecular weight of 100,000 to 1,000,000g/mol, the polyurethane has a number average molecular weight of 15,000 to 100,000g/mol, and the polyacrylic has a number average molecular weight of 10,000 to 1,200,000g/mol.
In the present application, the number average molecular weight is determined by Gel Permeation Chromatography (GPC) according to GB/T21863-2008 Gel Permeation Chromatography (GPC) using tetrahydrofuran as eluent (equivalent to German standard DIN 55672-1:2007 Gel Permeation Chromatography (GPC) part 1: tetrahydrofuran (THF) as eluting solvent).
The hydrophobic main chain of cellulose is associated with residual water molecules in the electrode assembly (namely the electric core JR) by virtue of hydrogen bonds, so that the viscosity of the system is improved, and the cellulose is stably present in the water-based metal ion battery.
The silicate swells to form flocculent substance after absorbing water, has good suspension property and dispersibility, combines with a proper amount of water to form colloid, can release charged particles in water, increases the viscosity of the system, and stably exists in the water-based metal ion battery.
The hydrophobic part in polyurethane molecules is associated with the hydrophobic part in polymer emulsion molecules, emulsion particles and the like to form a three-dimensional network structure, high shear viscosity is provided, and the hydrophilic chains in the molecules are further thickened through hydrogen bonding produced by water molecules.
The polyacrylic acid powder is tightly contracted together before contacting with water, when the polyacrylic acid powder is dispersed in water, the cross-linked acrylic acid polymer starts to open, carboxyl groups are ionized to generate-COO-, repulsive force between negative charges enables the molecular structure to be completely unfolded, the fluidity is deteriorated, and the viscosity is increased.
In some embodiments, the thickener has a coating density of 0.1 to 0.3mg/1540.25mm 2, alternatively 0.1 to 0.2mg/1540.25mm 2, further alternatively 0.2mg/1540.25mm 2.
When the coating density of the thickener is too large, the function of the polymer coating is affected, and when the coating density of the thickener is too small, the effect cannot be exerted. Therefore, when the coating density of the thickener is within the range, the cycle performance and the safety performance of the aqueous metal ion battery can be further improved.
Although the units of coating density are sometimes expressed in "mg/1540.25mm 2", this expression is not intended to imply any particular requirement for area.
In some embodiments, the polymer coating has a coating density of 0.6 to 6.5mg/1540.25mm 2. When the coating density of the polymer coating is within the given range, good adhesion of the separator and the positive and negative pole pieces can be ensured.
In some embodiments, the thickener is present in the polymer coating in an amount of 1.5% to 50% by weight. When the weight percentage of the thickener in the polymer coating is within the given range, a better bonding effect can be achieved without affecting the function of the polymer coating.
In some embodiments, the ceramic coating has a thickness of 0.5 to 4 μm.
In some embodiments, the ceramic coating comprises ceramic particles in an amount of 60-98% by weight and a binder in an amount of 2-40% by weight.
In some embodiments, the ceramic particles are selected from at least one of boehmite (γ -AlOOH), alumina (Al 2O3), barium sulfate (BaSO 4), magnesium oxide (MgO), magnesium hydroxide (Mg (OH) 2), silica (SiO 2), tin dioxide (SnO 2), titanium oxide (TiO 2), calcium oxide (CaO), zinc oxide (ZnO), zirconium oxide (ZrO 2), yttrium oxide (Y 2O3), nickel oxide (NiO), cerium oxide (CeO 2), zirconium titanate (SrTiO 3), barium titanate (BaTiO 3), magnesium fluoride (MgF 2).
In some embodiments, the binder is selected from at least one of polyvinylidene fluoride, polyacrylate, polymethyl methacrylate, polyacrylonitrile, polyimide, polyethylene oxide, polyvinyl alcohol.
In some embodiments, the polymer coating thickness is 1-20 μm.
In some embodiments, the polymeric coating comprises a polymer that is PVDF and an aqueous thickener in an amount of 50% to 98.5% by weight of the polymer and in an amount of 1.5% to 50% by weight of the aqueous thickener.
In some embodiments, the substrate is selected from at least one of glass fiber, nonwoven, polyethylene, and polypropylene.
In some embodiments, the substrate has a thickness of 5 to 30 μm.
In some embodiments, the aqueous metal ion battery is an aqueous sodium ion battery, an aqueous lithium ion battery, an aqueous zinc ion battery, or an aqueous aluminum ion battery.
In one embodiment, the present application provides a method of making an aqueous metal ion battery comprising a separator comprising:
A substrate;
a ceramic coating on at least one surface of the substrate, and
A polymer coating on the ceramic coating,
The polymeric coating layer comprises a thickener which,
The method for preparing the water-based metal ion battery comprises the following steps:
(1) Preparing a positive electrode plate;
(2) Preparing a negative electrode plate;
(3) Preparing a diaphragm;
(4) Preparing an electrolyte;
(5) Preparing a water-based metal ion battery;
wherein, step (3) includes:
(3-1) providing a substrate,
(3-2) Providing a ceramic slurry, coating and drying the ceramic slurry on at least one surface of the substrate to form a ceramic coating, and
(3-3) Providing a polymer slurry containing a thickener, coating the polymer slurry on the ceramic coating layer and drying to form a polymer coating layer, thereby obtaining a separator.
Therefore, the method disclosed by the application comprises the thickening agent in the polymer coating of the water-based metal ion battery diaphragm in a simple manner, and the viscosity of the water-based metal ion battery diaphragm can be increased after water absorption, so that the bonding between the diaphragm and the positive and negative pole pieces is enhanced.
In some embodiments, in step (3-2), the coating may be gravure coating using a coater comprising gravure rolls having a line count of 50-400LPI and a gravure coating speed of 5-60m/min.
In some embodiments, in step (3-2), the ceramic slurry has a solids content of 50-70%.
In some embodiments, in step (3-2), the temperature of drying is 30-70 ℃.
In some embodiments, in step (3-3), the coating is a spray coating at a rate of 0.01-0.1mL/min/mm 2.
In some embodiments, in step (3-3), the temperature of drying is 30-70 ℃.
The aqueous metal ion battery and the electric device according to the present application will be described below with reference to the drawings.
Typically, an aqueous metal ion battery includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The diaphragm is arranged between the positive pole piece and the negative pole piece, mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and can enable ions to pass through. The positive electrode sheet, the negative electrode sheet and the electrolyte can be prepared from the existing products for metal ion batteries.
[ Positive electrode sheet ]
The positive pole piece comprises a positive current collector and a positive film layer arranged on at least one surface of the positive current collector, wherein the positive film layer comprises a positive active material.
As an example, the positive electrode current collector has two surfaces opposing in its own thickness direction, and the positive electrode film layer is provided on either one or both of the two surfaces opposing the positive electrode current collector.
In some embodiments, the positive current collector may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the positive electrode active material may employ a positive electrode active material for aqueous metal ion batteries, as known in the art. As an example, for aqueous lithium ion batteries, the positive electrode active material may include at least one of olivine structured lithium-containing phosphates, lithium transition metal oxides, and their respective modified compounds. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery positive electrode active material may be used. These positive electrode active materials may be used alone or in combination of two or more. Examples of lithium transition metal oxides include, but are not limited to, lithium cobalt oxide (e.g., liCoO 2), lithium nickel oxide (e.g., liNiO 2), lithium manganese oxide (e.g., liMnO 2、LiMn2O4), lithium nickel cobalt oxide, Lithium manganese cobalt oxide, lithium nickel manganese oxide, Lithium nickel cobalt manganese oxide (such as LiNi 1/3Co1/ 3Mn1/3O2 (which may also be abbreviated as NCM 333)、LiNi0.5Co0.2Mn0.3O2 (which may also be abbreviated as NCM 523)、LiNi0.5Co0.25Mn0.25O2 (which may also be abbreviated as NCM 211)、LiNi0.6Co0.2Mn0.2O2 (which may also be abbreviated as NCM 622)、LiNi0.8Co0.1Mn0.1O2 (which may also be abbreviated as NCM 811)), a metal oxide, At least one of lithium nickel cobalt aluminum oxide (such as LiNi 0.85Co0.15Al0.05O2) and modified compounds thereof, and the like. Examples of olivine structured lithium-containing phosphates may include, but are not limited to, at least one of lithium iron phosphate (such as LiFePO 4 (which may also be referred to simply as LFP)), a composite of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4), a composite of lithium manganese phosphate and carbon, lithium manganese phosphate, a composite of lithium manganese phosphate and carbon. For aqueous sodium ion batteries, the positive electrode active material may include at least one of Na 0.44MnO2、NaMnO2、V2O5 and the like. For aqueous zinc ion batteries, the positive electrode active material may include at least one of MnO 2、VO2、V2O3、V2O5, prussian blue, and the like. For aqueous aluminum ion batteries, the positive electrode active material may include at least one of natural graphite, expanded commercial graphite, feS 2、V2O5、TiO2, and the like.
In some embodiments, the positive electrode active material is present in the positive electrode film layer in an amount of 70-98 wt%, based on the total weight of the positive electrode film layer.
In some embodiments, the positive electrode film layer further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluoroacrylate resin.
In some embodiments, the binder comprises 0.1 to 15% by mass of the positive electrode film layer.
In some embodiments, the positive electrode film layer further optionally includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the conductive agent comprises 1-15% by mass of the positive electrode film layer.
In some embodiments, the positive electrode sheet may be prepared by dispersing the above-described components for preparing a positive electrode sheet, such as a positive electrode active material, a conductive agent, a binder, and any other components, in a solvent (e.g., N-methylpyrrolidone) to form a positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, and performing processes such as drying, cold pressing, and the like to obtain the positive electrode sheet.
[ Negative electrode sheet ]
The negative electrode plate comprises a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector, wherein the negative electrode film layer comprises a negative electrode active material.
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode film layer is provided on either one or both of the two surfaces opposing the anode current collector.
In some embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the anode active material may employ an anode active material for a battery, which is well known in the art. As an example, for an aqueous lithium ion battery, the negative electrode active material may include at least one of artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based material, tin-based material, lithium titanate, and the like. The silicon-based material may be at least one selected from elemental silicon, silicon oxygen compounds, silicon carbon composites, silicon nitrogen composites, and silicon alloys. The tin-based material may be at least one selected from elemental tin, tin oxide, and tin alloys. For aqueous sodium ion batteries, the negative electrode active material may include at least one of activated carbon, naTi 2(PO4)3, polyimide (PI), and the like. For aqueous zinc ion batteries, the negative active material may be metallic zinc. For aqueous aluminum ion batteries, the negative electrode active material may be metallic aluminum. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery anode active material may be used. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments, the negative electrode active material comprises 75% to 99%, alternatively 80% to 98%, by mass of the negative electrode film layer.
In some embodiments, the negative electrode film layer further optionally includes a binder. The binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
In some embodiments, the binder comprises 0.1% to 3.5%, optionally 0.5% to 2.5% by mass of the negative electrode film layer.
In some embodiments, the negative electrode film layer further optionally includes a conductive agent. The conductive agent is at least one selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
In some embodiments, the conductive agent comprises 0.1% to 5%, optionally 0.3% to 3% by mass of the negative electrode film layer.
In some embodiments, the negative electrode film layer may optionally further include other adjuvants, such as thickening agents (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
In some embodiments, the negative electrode tab may be prepared by dispersing the above components for preparing the negative electrode tab, such as the negative electrode active material, the conductive agent, the binder, and any other components, in a solvent (e.g., deionized water) to form a negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, and performing processes such as drying, cold pressing, and the like to obtain the negative electrode tab.
[ Electrolyte ]
The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The application is not particularly limited in the kind of electrolyte, and may be selected according to the need. For example, the electrolyte may be liquid, gel, or all solid.
In some embodiments, the electrolyte is an electrolyte. The electrolyte comprises electrolyte salt and a solvent, wherein in the water-based metal ion battery, the solvent is water.
In some embodiments, for aqueous lithium ion batteries, the electrolyte salt may be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis-fluorosulfonyl imide, lithium bis-trifluoromethylsulfonyl imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorooxalato phosphate, and lithium tetrafluorooxalato phosphate. For aqueous sodium ion batteries, the electrolyte salt may be selected from sodium hexafluorophosphate (NaPF 6), sodium perchlorate (NaClO 4), and the like. For aqueous zinc ion batteries, the electrolyte salt may be selected from zinc sulfate, zinc tetrafluoroborate, zinc nitrate, zinc chloride. For aqueous aluminum ion batteries, the electrolyte salt may be selected from AlCl 3、Al2(SO4)3、Al(NO3)3 and the like.
In some embodiments, the concentration of the electrolyte salt is, for example, 0.3mol/L (mol/L) or more, alternatively 0.7mol/L or more, 1.7mol/L or less, alternatively 1.2mol/L or less.
In some embodiments, the electrolyte further optionally includes an additive. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives capable of improving certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high or low temperature performance of the battery, and the like.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator may be fabricated into an electrode assembly (i.e., the cell JR) through a winding process or a lamination process.
As shown in fig. 1, the electrode assembly includes a positive electrode tab, a negative electrode tab, and a separator. Wherein the separator comprises a substrate, a ceramic coating, and a polymer coating, the polymer coating comprising a thickener.
In some embodiments, the thickness of the electrode assembly (i.e., the cell JR) is 5-60mm.
In some embodiments, the aqueous metal ion battery may include an outer package. The outer package may be used to encapsulate the electrode assembly and electrolyte described above.
In some embodiments, the outer package of the aqueous metal ion battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, or the like. The outer package of the aqueous metal ion battery may be a pouch, for example, a pouch-type pouch. The material of the flexible bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
The shape of the aqueous metal ion battery is not particularly limited, and may be cylindrical, square or any other shape. For example, fig. 2 shows an aqueous metal ion battery 5 having a square structure as an example.
In some embodiments, referring to fig. 3, the outer package may include a housing 51 and a cover 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, where the bottom plate and the side plate enclose a receiving chamber. The housing 51 has an opening communicating with the accommodation chamber, and the cover plate 53 can be provided to cover the opening to close the accommodation chamber. The positive electrode sheet, the negative electrode sheet, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process. The electrode assembly 52 is enclosed in the accommodating chamber. The electrolyte is impregnated in the electrode assembly 52. The number of electrode assemblies 52 included in the aqueous metal-ion battery 5 may be one or more, and those skilled in the art may choose the number according to specific practical requirements.
The aqueous metal ion battery may be in the form of a battery cell, a battery module, or a battery pack, for example. The battery module and the battery pack include battery cells, and the battery pack may include the battery module.
In some embodiments, the aqueous metal ion battery in the form of a battery cell may be assembled into a battery module, and the number of aqueous metal ion batteries in the form of a battery cell contained in the battery module may be one or more, and the specific number may be selected by one skilled in the art according to the application and capacity of the battery module.
Fig. 4 is a battery module 4 as an example. Referring to fig. 4, in the battery module 4, a plurality of aqueous metal ion batteries 5 in the form of battery cells may be arranged in order along the longitudinal direction of the battery module 4. Of course, the arrangement may be performed in any other way. The aqueous metal ion battery 5 in the form of the plurality of battery cells may be further fixed by fasteners.
Alternatively, the battery module 4 may further include a housing having an accommodation space in which a plurality of aqueous metal ion batteries 5 in the form of battery cells are accommodated.
In some embodiments, the above battery modules may be further assembled into a battery pack, and the number of battery modules included in the battery pack may be one or more, and a specific number may be selected by those skilled in the art according to the application and capacity of the battery pack.
Fig. 5 and 6 are battery packs 1 as an example. Referring to fig. 5 and 6, a battery case and a plurality of battery modules 4 disposed in the battery case may be included in the battery pack 1. The battery box includes an upper box body 2 and a lower box body 3, and the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4. The plurality of battery modules 4 may be arranged in the battery box in any manner.
In addition, the application also provides an electric device which comprises at least one of the battery cell, the battery module or the battery pack. The battery cell, the battery module, or the battery pack may be used as a power source of the power device, and may also be used as an energy storage unit of the power device. The power utilization device may include mobile devices (e.g., cell phones, notebook computers, etc.), electric vehicles (e.g., electric-only vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but is not limited thereto.
As the electricity consumption device, a battery cell, a battery module, or a battery pack may be selected according to the use requirements thereof.
Fig. 7 is an electrical device as an example. The electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or the like. In order to meet the requirements of the electric device for high power and high energy density of the water-based metal ion battery, a battery pack or a battery module can be adopted.
As another example, the device may be a cell phone, tablet computer, notebook computer, or the like. The device is generally required to be light and thin, and a battery cell can be used as a power supply.
Examples
Hereinafter, embodiments of the present application are described. The following examples are illustrative only and are not to be construed as limiting the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
(1) Preparation of positive electrode sheet
Uniformly mixing an anode active material Na 0.44MnO2, PVDF and conductive agent carbon black in a proper amount of solvent N-methyl pyrrolidone (NMP) according to a weight ratio of 8:1:1 to obtain anode slurry, coating the anode slurry on an anode current collector aluminum foil, and obtaining an anode plate through the procedures of drying, cold pressing, slitting and cutting. The surface density of the positive pole piece is 2.5mg/mm 2, and the compacted density is 2.0g/cm 3;
(2) Preparation of negative electrode sheet
Uniformly mixing negative electrode active material active carbon, conductive agent carbon black, binder Styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC-Na) in a proper amount of solvent deionized water according to a weight ratio of 90:5:3.1:1.9 to obtain negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector copper foil, and obtaining a negative electrode plate through the procedures of drying, cold pressing, slitting and cutting. The surface density of the negative pole piece is 1.45mg/mm 2, and the compaction density is 1.5g/cm 3;
(3) Preparation of separator
(3-1) Providing a Polyethylene (PE) film having a thickness of 7 μm as a substrate,
(3-2) Uniformly mixing ceramic particles Al 2O3 and a binder PVDF in a proper amount of solvent deionized water according to a weight ratio of 7:1 to obtain ceramic slurry with a solid content of 60%, coating the ceramic slurry on two surfaces of the substrate by using a coating machine, and drying to form a ceramic coating with a single-sided thickness of 2 μm. Wherein the number of lines of gravure roll of the coater was 150LPI, the coating speed was 10m/min, the drying temperature was 40℃and the drying time was 2 hours, and
(3-3) Uniformly mixing polymer PVDF and sodium polyacrylate (with a number average molecular weight of 15,000 g/mol) according to a weight ratio of 6:1 to obtain polymer slurry, spraying the polymer slurry onto the ceramic coating, and drying to form an island-shaped polymer coating, thereby obtaining the diaphragm. The weight and the thickness of the polymer coating on the two sides are consistent, the spraying speed is 0.3mL/min/mm 2, the coating density of the polymer coating is 1.4mg/1540mm 2, the coating density of the sodium polyacrylate is 0.2mg/1540mm 2, the drying temperature is 40 ℃, and the drying time is 5 hours, so that the diaphragm is obtained;
(4) Preparation of electrolyte
Providing as an electrolyte an aqueous Na 2SO4 solution having a concentration of 1M at ph=7;
(5) Preparation of aqueous Metal ion Battery
Sequentially stacking the positive electrode plate, the diaphragm and the negative electrode plate, enabling the diaphragm to be positioned between the positive electrode plate and the negative electrode plate to play a role of isolation, then winding to obtain an electrode assembly (the thickness of the electrode assembly is 25 mm), placing the electrode assembly in an outer package, injecting the prepared electrolyte into a dried secondary battery, and carrying out vacuum packaging, standing, formation and shaping procedures to obtain the water-based sodium ion battery, wherein the capacity of the water-based sodium ion battery is 71Ah.
Examples 2 to 4
The preparation of the aqueous sodium-ion battery of examples 2-4 was similar to the preparation method of the aqueous sodium-ion battery of example 1, except that the mass ratio of each substance in the polymer slurry was adjusted so that the coating density of sodium polyacrylate was 0.1mg/1540mm 2、0.3mg/1540mm2 and 0.4mg/1540mm 2, respectively.
Examples 5 to 7
The aqueous sodium-ion batteries of examples 5-7 were prepared similarly to the aqueous sodium-ion battery of example 1, except that sodium polyacrylate was replaced with methylcellulose (number average molecular weight 200,000 g/mol), aluminum silicate, and polyurethane (number average molecular weight 35,000g/mol, available from rommends company, usa), respectively.
Examples 8 to 9
The aqueous sodium-ion batteries of examples 8-9 were prepared similarly to the aqueous sodium-ion battery of example 1, except that the polymer coatings had a coating density of 6.5mg/1540mm 2 and 0.6mg/1540mm 2, respectively, and the thickeners had a coating density of 0.1mg/1540mm 2 and 0.3mg/1540mm 2, respectively.
Comparative example 1
The preparation of the aqueous sodium-ion battery of comparative example 1 was similar to the preparation method of the aqueous sodium-ion battery of example 1, except that sodium polyacrylate was not added in step (3-3), and the coating density of the polymer coating was 1.5mg/1540mm 2.
3. Performance testing
1. Method for testing temperature of inner ring of electrode assembly after cooling for 4 minutes
And arranging a temperature sensing wire TT-K-40-SLE-15 on the inner ring of the electrode assembly, and detecting the temperature of the innermost ring of the electrode assembly after cooling for 4 minutes.
2. Capacity retention rate test method
In an environment of 25 ℃, the first charge and discharge are performed, and constant-current and constant-voltage charge is performed at a charging current equivalent to 2.2C until the upper limit voltage is 2V. Then, constant current discharge was performed at a discharge current of 1C until the final voltage was 0.5V, and the first discharge capacity value Cn was recorded. Then charge and discharge cycles of 2.2Cn/1Cn,0.5-2.0V were performed continuously, discharge capacity values during the cycles were recorded, and the cycle capacity retention was calculated. Capacity retention rate of nth cycle= (discharge capacity of nth cycle/discharge capacity of first cycle) ×100%.
3. Method for testing wrinkling degree
The secondary battery was subjected to a cyclic charge and discharge procedure, the charge and discharge currents were 2.2C and 1C, respectively, and the number of cycles was 2000 cycles. And after the cyclic charge and discharge procedure is finished, the secondary battery is disassembled, and the wrinkling degree of the negative electrode plate is evaluated.
The wrinkle degree evaluation method is as follows:
no wrinkling: single electrode Assembly No wrinkling zone
Primary wrinkling, wherein the maximum area of a single wrinkling region is less than or equal to 5 multiplied by 5mm 2, and the number of the wrinkling regions of a single electrode assembly is less than or equal to 1;
Secondary wrinkling, wherein 5×5mm 2 < maximum area of single wrinkling area is less than or equal to 10×10mm 2, and number of wrinkling areas of single electrode assembly is less than or equal to 1;
and three stages of wrinkling, namely, failing to meet the first two stages of judging conditions.
The above examples and comparative examples were tested according to the procedure described above, respectively, with specific values as indicated in table 1.
As can be seen from table 1, the present application can significantly improve the cycle performance and/or safety performance of the aqueous metal ion battery by using the thickener in the polymer coating layer of the separator. In particular, by further selecting the coating density of the thickener, the coating density of the polymer coating and the weight percentage of the thickener, the cycle performance and/or the safety performance thereof can be further improved. In contrast, comparative example 1, in which the polymer coating of the separator did not contain a thickener, was inferior in both cycle performance and safety performance as in examples 1-9.
The present application is not limited to the above embodiment. The above embodiments are merely examples, and embodiments having substantially the same configuration and the same effects as those of the technical idea within the scope of the present application are included in the technical scope of the present application. Further, various modifications that can be made to the embodiments and other modes of combining some of the constituent elements in the embodiments, which are conceivable to those skilled in the art, are also included in the scope of the present application within the scope not departing from the gist of the present application.
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| CN109935769A (en) * | 2018-12-29 | 2019-06-25 | 深圳中兴新材技术股份有限公司 | A kind of electrolyte resistance ceramic-coated separator and preparation method thereof |
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