CN115189013A - Sodium ion battery and preparation method thereof - Google Patents
Sodium ion battery and preparation method thereof Download PDFInfo
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- CN115189013A CN115189013A CN202210755599.4A CN202210755599A CN115189013A CN 115189013 A CN115189013 A CN 115189013A CN 202210755599 A CN202210755599 A CN 202210755599A CN 115189013 A CN115189013 A CN 115189013A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M2010/4292—Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode
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- 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
Abstract
The invention discloses a sodium ion battery, which comprises a positive pole piece and a negative pole piece, wherein the designed capacity value of the negative pole piece is smaller than the capacity of the positive pole piece by controlling the capacity ratio N/P of the positive pole piece and the negative pole piece, so that part of sodium ions are firstly embedded into active substances of the negative pole piece in the charging process of the battery, and because the designed capacity of the negative pole piece is smaller than the capacity of the positive pole piece, enough space for accommodating the sodium ions from the positive pole piece is not available in the active substances of the negative pole piece, and the sodium ions are separated out in the pores of the negative pole piece in a sodium metal particle mode in the continuous charging process and exist in the pores of the negative pole piece in a granular solid sodium metal mode. The invention improves the weight ratio energy of the negative electrode, reduces the weight of the negative electrode pole piece and the thickness of the pole piece, improves the energy density of the sodium-ion battery and reduces the cost.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a sodium ion battery and a preparation method thereof.
Background
The sodium ion battery is hopeful to replace the lithium ion battery in some application fields by virtue of the advantages that the sodium ion battery is not limited by resources, has good potential low-temperature performance and the like, such as the application fields with low energy density requirement, such as data centers, communication base stations, large-scale energy storage fields, non-subsidy electric vehicles, low-temperature application fields and the like.
Sodium Ion batteries belong to a relatively new discipline, the scientific principles and so on of which are still under investigation, such as the mechanism of Storage of sodium ions inside hard charcoal, which is currently controversial in academic circles both at home and abroad, but as these 3 academic papers (1. New mechanical instruments on Na-Ion Storage in a non-productive carbon.c. bommiemiemer et al/Nano lett.2015,15,5888-5892, 2.regenerative science with Storage mechanism in hard carbon.s. acquisition et al/Carbon 145 (2019) 67-81. Hard Carbon for sodium-batteries 20120123, structural, analytical, and electrochemical. Summarized (shown in fig. 10), the stored physicochemical environment of sodium ions in hard Carbon can exist in the interior of hard Carbon in three ways, (1) the edges and defect points of the Carbon surface, (2) the closed angstrom-scale (or sub-nanometer-scale) voids formed by disordered stacking of graphene sheet layers (turbo-graphitic domains, TN), sodium ions filling sodium metal clusters formed in angstrom-scale (or sub-nanometer-scale) voids, and (3) the interlayer spacing voids between graphene sheet layers of turbo-graphitic domains. Graphene sheets (Graphene) having sp 2 The hybridized and connected carbon atoms are tightly packed into a single-layer two-dimensional honeycomb lattice structure. The carbon atom has 4 valence electrons, wherein 3 electrons generate sp2 bonds, that is, each carbon atom contributes an unbound electron on the pz orbital, the pz orbitals of neighboring atoms form pi bonds in a direction perpendicular to the plane, and the newly formed pi bonds are in a half-filled state. Research proves that the coordination number of carbon atoms in the graphene is 3, and the bond length between every two adjacent carbon atoms is 1.42 multiplied by 10-10 metersThe angle between the keys is 120 deg.. In addition to the honeycomb-type layered structure in which the σ bond links other carbon atoms into hexagonal rings, the pz orbit of each carbon atom perpendicular to the layer plane can form a large-pi bond (similar to a benzene ring) of multiple atoms throughout the entire layer, and thus has excellent conductivity properties.
The definition of a physical cluster is: clusters are relatively stable microscopic or submicroscopic aggregates composed of several or even thousands of atoms, molecules or ions by physical or chemical bonding forces, and are new levels of material structure between atoms, molecules and macroscopic solid matter, representing the initial state of condensed matter. Clustering is widely present in nature and in human practical activities, and research on clustering has led to the discovery, understanding, and use of new growth points for this material science. The spatial scale of a cluster is in the range of a few angstroms to hundreds of angstroms, and is too large when described as an inorganic molecule, too small when described as a small solid, and many properties are different from a single atomic molecule, and different from solid and liquid, and cannot be obtained by simple linear epitaxy or interpolation of both properties. Therefore, clusters are considered as a new layer of material structure between atoms, molecules and macroscopic solid matter, and are transition states of various materials from atomic molecules to bulk materials, or represent initial states of condensed materials. The basic problem of cluster science research is to figure out how clusters evolve from atoms, molecules, step by step, and with this evolution, how the structure and properties of the clusters change, particularly when the size is large, transitioning to macroscopic solids. Cluster science is in the category of multidisciplinary crossings. Concepts and methods of atomic molecular physics, condensed state physics, quantum chemistry, structural chemistry, atomic cluster chemistry, surface science, material science and other disciplines are interwoven together, forming the central issue of current cluster research, and developing into a novel discipline between atomic molecular physics and solid physics.
Sodium metal clusters are relatively stable microscopic or submicroscopic aggregates composed of several to hundreds of atoms, molecules, or ions, by physical or chemical bonding forces, the physical and chemical properties of which vary with the number of atoms contained. Clustering is a concept of material scale angstrom, sub-nanometer materials. The spatial scale of a cluster is in the range of a few angstroms to hundreds of angstroms, and is too small for description with inorganic molecules, too large for description with small solid masses, many properties that differ from single atomic molecules, from solids and liquids, and cannot be obtained with simple linear epitaxy or interpolation of both properties. Therefore, clusters are considered as a new layer of material structure between atoms, molecules and macroscopic solid matter, and are transition states of various materials from atomic molecules to bulk materials, or represent initial states of condensed materials.
The nano metal particles (existing in the pores of the coating of the pole piece and formed by solid particles of active substance hard carbon, conductive agent, adhesive and the like) proposed in the invention are solid metals with the size of micron, are a general solid metal concept and are essentially different from sodium metal clusters.
Regarding the porosity of the electrode plate, the sodium ion battery electrode plate is a coating layer formed by powder particles (such as hard carbon active substance powder, powder particles of a conductive agent and the like) and an adhesive, and the surface of the powder particles is rough and irregular, and when the powder particles are stacked, pores are formed between the particles, so that the porosity of the electrode plate coating layer is about 30%. When the densities of the active material, the conductive agent, and the binder are all calculated using true densities, the calculated porosities are the pores between the particles, excluding the angstrom (sub-nanometer) pores inside the active material particles.
In general, the pore size of the battery electrode sheet is multi-scale, and generally, the pores formed between the hard carbon of the active material and the solid particles of the conductive agent, the adhesive and the like are in the micron to submicron scale, while the internal pores of the hard carbon particles of the active material are in the angstrom to sub-nanometer scale.
The porosity is the percentage of the volume of pores formed among active substance hard carbon, conductive agent, adhesive and other solid particles in the electrode plate to the total volume of the electrode plate (excluding angstrom-scale to sub-nanometer-scale pores inside active substance hard carbon particles), and the porosity of the electrode plate directly reflects the degree of compaction of the electrode plate and is closely related to the compaction density value. The porosity of the electrode piece is shown as the formula (1):
porosity =1-Vi/V
In the formula: vi represents the sum of the volumes of the solid phase components of the coating of the pole piece (not containing the metallic current collector), including the volumes of the solid components of the active material, binder and conductive agent, etc.; v represents the overall volume of the pole piece coating. The volume of each component is the value of the weight of each component divided by the true density of each component, and the volume of the coating can be obtained by dividing the weight of the coating of the pole piece by the compacted density of the pole piece, which is obtained by dividing the areal density of the pole piece by the thickness of the pole piece.
The following figure is a schematic diagram of the storage mechanism of sodium ions in hard carbon summarized and proposed by the present invention, and is shown in figure 10.
The sodium ion battery of the invention usually adopts a hard carbon cathode, and is different from a graphite cathode adopted by a lithium ion battery in that the radius of sodium ions is 0.102nm and is larger than that of lithium ions (0.076 nm), and the sodium ions with larger radius can be embedded between graphite layers only under the conditions of assisting by ether solvents and increasing the heat power Gibbs energy and can cause the expansion of the volume of graphite more than 100 percent, so the graphite cathode used by the traditional lithium ion battery can not be used as the cathode of the sodium ion battery. Therefore, it is necessary to find a carbon material capable of intercalating sodium ions, and a hard carbon material has a low true density value (the true density of the hard carbon is 1.45 g/cm) 3 The microvoids formed by disordered stacking of turbine graphite domains formed by graphene sheets in the hard carbon are far larger than the orderly stacked microvoids of graphene sheet layers in the graphite, and the true density value of the graphite is 2.2g/cm 3 The graphene sheet layers inside the graphite active material are stacked in order, the inner space of the graphene sheet layers is much smaller than that of hard carbon by about 34%, and the true density ratio of the hard carbon to the graphite is as follows: 1.45/2.2= 65.9%), sodium ions can be embedded in the sodium metal clusters formed in the angstrom-scale (or sub-nanometer) gaps between the disordered turbine-like graphite domains formed by graphene sheets in the hard carbon material within the effective potential window, or embedded in the hard carbon materialIn the graphene sheet interlamellar spacing of the graphene sheet turbine-like graphite domain in the material, the hard carbon material is selected as the preferred negative active material for sodium intercalation because the hard carbon has large sodium intercalation void space. At present, the research direction of the negative electrode material of the sodium ion battery is hard carbon, titanium-based oxide and alloy, phosphorus carbon or metal phosphide and sodium metal phosphide materials and the like, and the sodium ion battery which has the most research on hard carbon and is commercialized at present also takes the hard carbon material as the negative electrode. However, the gram capacity of the hard carbon negative electrode used in the sodium ion battery is lower than that of graphite, and the cost is high, so that the energy density of the sodium ion battery needs to be further improved and the cost needs to be further reduced.
Therefore, a sodium ion battery and a preparation method thereof are provided to solve the above problems.
Disclosure of Invention
The invention aims to provide a sodium ion battery, which comprises a positive pole piece and a negative pole piece, wherein the designed value of the capacity of the negative pole piece is smaller than the capacity of the positive pole piece by controlling the N/P ratio of the capacity of the positive pole piece and the capacity of the negative pole piece, so that a part of sodium ions are firstly embedded into active substance hard carbon particles of the negative pole piece in the charging process of the battery, and because the designed capacity of the negative pole piece is smaller than the capacity of the positive pole piece, the active substance hard carbon of the negative pole piece has insufficient space for accommodating the sodium ions from the positive pole piece, the sodium ions are separated out in the pores of the negative pole piece in a sodium metal particle mode in the continuous charging process and exist in the pores of the negative pole piece in a granular solid sodium metal mode, and after the charging is finished, the negative electrode end becomes an alloy pole piece formed by compounding sodium ions and sodium metal cluster groups and granular solid sodium metal and a hard carbon negative electrode, namely an alloy formed by embedding the sodium ions into a hard carbon active substance existing with sodium metal clusters and a compound negative pole piece formed by existing the granular solid sodium metal in pores of a negative pole piece coating, the obtained sodium ion battery is a compound sodium battery of a sodium ion/sodium metal cluster-hard carbon alloy battery and a granular solid sodium metal battery, the battery can be used as a secondary rechargeable sodium ion battery and a primary sodium metal battery, the rated voltage is 1.5-3.5V, the battery can be used for replacing a high-cost lithium metal primary battery, and also becomes an electrochemical device of the compound sodium battery of the hard carbon type sodium ion battery and the granular sodium metal battery.
Further, the negative electrode material is a hard carbon material or other types of sodium-embedded materials, the sodium-embedded materials are one or more of titanium-based layered oxides, tin alloys, phosphides or phosphorus carbon and pre-sodium phosphorus carbon materials, the phosphorus carbon material is a compound coated by nano-particle phosphorus and carbon, and the phosphides are Sn3P4, sbP or the pre-sodium phosphorus carbon material.
Further, the positive electrode material is one of a sodium salt of a multi-component layered oxide, prussian white, sodium manganate and a polyanion sodium salt, and the polyanion sodium salt is one of a phosphate and a sulfate sodium compound (such as sodium ferric pyrophosphate, sodium vanadium phosphate, sodium ferric sulfate and the like).
Further, the preparation steps for the prussian sodium positive electrode comprise:
the method comprises the following steps: preparation of deoxygenated water: continuously injecting nitrogen into deionized water for more than one hour to remove oxygen in the water, or heating the deionized water to 100 ℃ and vacuumizing and stirring to remove oxygen in the water, or coexisting broken iron pins and the water for more than 24 hours to remove oxygen in the water, so as to obtain deoxygenated water;
step two: preparing slurry of the Prussian white positive electrode and a positive electrode piece: preparing anode slurry by using prepared deoxygenated water, stirring under vacuum pumping or under the protection of inert gas, vacuumizing and drying the prepared pole piece for at least 4 hours at the temperature higher than 150 ℃ to remove crystal water of active substances in the anode piece or vacuumizing and drying the prepared battery cell for at least 4 hours at the temperature higher than 150 ℃ before electrolyte injection to remove crystal water of the active substances in the anode piece to obtain an anode active material layered oxide, dissolving and uniformly mixing the anode active material layered oxide, a binder and a conductive agent in NMP according to a certain mass ratio, dispersing, preparing the anode slurry, coating the anode slurry on a current collector, drying, and rolling and forming.
Step three: adding a conductive agent, an adhesive and a solvent into the negative electrode pole piece to prepare negative slurry, coating the negative slurry on a current collector, drying and then rolling and forming;
step four: preparing an electrolyte: the electrolyte is dissolved in an electrolyte solvent to obtain an electrolyte.
Step five: assembling a full battery: cutting the positive pole piece, the negative pole piece and the diaphragm into corresponding sizes, winding the cut positive pole piece, the negative pole piece and the diaphragm into dry cells by a winding machine, and then performing welding, aluminum plastic film packaging, high-temperature baking, liquid injection, formation, air exhaust, secondary packaging, formation and capacity grading process flow to prepare the cylindrical soft package sodium ion composite battery.
Furthermore, the current collectors of the positive and negative pole pieces are at least one of a metal foil, a foam current collector, a metal mesh current collector, a carbon felt current collector, a carbon cloth current collector and a carbon paper current collector.
Further, the conductive agent includes at least one of conductive carbon black, graphite, carbon fiber, single-walled carbon nanotube, multi-walled carbon nanotube, graphene, and fullerene.
Furthermore, the compaction density of the negative pole piece is 0.5-1.8, the internal porosity of the pole piece is 1-99%, and the thickness of the coating of the negative pole piece containing active substances is more than 10 microns.
Further, the base material of the diaphragm is olefin, the olefin is one of polyethylene and polypropylene or a polyimide PI high-temperature diaphragm, a paper fiber or a glass fiber woven high-temperature diaphragm, at least one surface of the base material layer of the diaphragm is coated with a surface treatment layer, and the surface treatment layer is one of a polymer layer, an inorganic layer or a layer formed by a composite polymer and an inorganic substance.
Furthermore, the electrolyte can be at least one of sodium perchlorate, sodium hexafluorophosphate, sodium bifluorosulfonimide, sodium bifluoromethane sulfonylimide, sodium trifluoromethanesulfonate, sodium tetrafluoroborate, sodium difluorophosphate, sodium tetraphenylborate and sodium chloride.
Further, the electrolyte solvent is fluorinated carbonate (for example, fluorinated carbonate is 3, 3-trifluoropropyl carbonate, fluoroethylene carbonate, methyl 2, 2-trifluoroethyl carbonate), 1, 3-dioxolan-2-one, 4- [2, 3-tetrafluoro-2- (trifluoromethyl) propyl ], ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, propylene carbonate, methyl acetate, ethyl propionate, fluoroethylene carbonate, or diethyl ether, ethylene glycol dimethyl ether, 1, 3-dioxolane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, methyl tert-butyl ether, hydrofluoroether, fluoroether D2, preferably, at least one of ether solvent or fluoroether, fluorinated carbonate solvent is selected, and the electrolyte concentration is 0.1 to 5mol.
Compared with the prior art, the invention has the following beneficial effects:
compared with the conventional pure sodium metal pole piece battery, the sodium ion battery has great advantages, sodium metal particles in the composite pole piece are naturally formed in the battery formation charging process, no special anhydrous and anaerobic environment is needed, the pure sodium metal pole piece is difficult to manufacture and high in cost, sodium metal is easy to oxidize in the air, and therefore the sodium metal pole piece must be processed in the anhydrous and anaerobic environment under the protection of inert gas, and sodium dendrite is easy to generate in circulation, so that the short circuit behavior of the battery is further caused;
the N/P ratio designed by the invention is less than 1, the capacity of the negative hard carbon substance is less than the positive capacity, so that part of the capacity of the negative pole piece is replaced by the sodium metal particles with higher theoretical specific capacity, the gravimetric specific capacity of the negative pole is improved, the weight of the negative pole piece is reduced, the thickness of the negative pole piece is also reduced, namely the energy density of the sodium ion full-cell can be improved by reducing the using amount of the active substance of the negative pole, in addition, the discharge multiplying power performance of the cell is improved by reducing the internal resistance of the cell, the conductivity of the negative pole piece is improved due to the excellent conductivity of sodium metal after the sodium metal particles are filled into the pores of the pole piece, the direct current internal resistance of the cell is also reduced, and the discharge multiplying power performance of the cell is improved.
Drawings
FIG. 1 is a schematic data diagram of a negative electrode tab in example 1 of the present invention;
FIG. 2 is a schematic structural view of a negative electrode tab in example 1 of the present invention;
FIG. 3 is a schematic diagram showing data of a positive electrode sheet in example 1 of the present invention;
fig. 4 is a schematic structural view of a positive electrode sheet in embodiment 1 of the present invention;
FIG. 5 is a data diagram of a negative electrode tab in comparative example 1 of the present invention;
FIG. 6 is a schematic view of the structure of a negative electrode sheet in comparative example 1 of the present invention;
FIG. 7 is a graph showing data of the positive electrode sheet in comparative example 1 of the present invention;
FIG. 8 is a schematic view showing the structure of a positive electrode sheet in comparative example 1 of the present invention;
fig. 9 is a cycle life test graph of example 1 of the present invention.
Fig. 10 is a schematic view showing the mechanism of sodium ion storage inside hard charcoal according to the present invention.
Detailed Description
The invention provides a sodium ion battery and a preparation method thereof;
1. the preparation and material selection of the negative electrode pole piece of the sodium ion battery are as follows:
the negative electrode pole piece can be manufactured by adding a conductive agent and a bonding agent into a hard carbon material, adding a proper solvent to prepare a negative electrode slurry, coating the negative electrode slurry on a current collector consisting of a metal base, drying and rolling and forming;
as the conductive agent, acetylene black, chlorophyll black, carbon nanofibers, carbon nanotubes, graphene, carbon fibers, or the like can be used, and the amount to be added varies depending on the kind of the conductive aid used, and the preferable ratio of the conductive aid to be added is 0.5 to 15% by weight, where the amount of hard carbon material + the amount of binder + the amount of conductive aid =100% by weight, more preferably 0.5 to 7% by weight, and particularly preferably 0.5 to 5% by weight;
the binder is not particularly limited if it does not react with an electrolyte such as PVDF, a composite of polytetrafluoroethylene, SBR and CMC, and PVDF, which is attached to the surface of the active material, hardly hinders the movement of sodium ions, is preferable for obtaining good input/output characteristics, and a polar solvent such as N-methylpyrrolidone is preferably used for dissolving PVDF to form a slurry. If the amount of the binder added is too small, the binding between the negative electrode material particles and the current collector is insufficient, and the preferable amount of the binder added varies depending on the type of the binder used, but the PVDF-based binder is preferably 0.5 to 10% by weight;
on the other hand, in the binder using water as a solvent, a plurality of binders such as a composite of SBR and CMC are often used in combination, and the total amount of the total binder used is preferably 0.5 to 5% (wt%), more preferably 1 to 4 wt%, and the electrode active material layer is formed substantially on both sides of the current collector, but if necessary, one side may be formed, and the thicker the electrode active material layer is, the less the current collector and the separator are, and therefore, it is preferable to increase the capacity, but the thinner the electrode active material layer is, the more favorable the input-output characteristics are, and therefore, if the active material layer is too thick, the input-output characteristics are degraded, and the thickness of the preferable one-side active material layer is not limited, and is in the range of 10 μm to 1000 μm, preferably 10 to 130 μm, more preferably 20 to 75 μm, and particularly 20 to 50 μm.
The negative electrode sheet generally has a current collector, and a foil of stainless steel, copper, aluminum, nickel or carbon can be used as the current collector, with copper foil or aluminum foil being preferred.
2. The preparation of the positive electrode pole piece of the sodium ion battery selects materials:
when the negative electrode material of the present invention is used to form a negative electrode sheet for a sodium ion secondary battery, the material is not particularly limited as to the positive electrode material, separator, electrolyte, and other materials of the battery, and various sodium-containing positive electrode materials, separators, electrolytes, and the like that are generally used for sodium ion secondary batteries can be used.
The positive electrode sheet may include a positive active material, a conductive additive, a binder, or both, and the composite ratio of the positive active material and other materials in the positive active material layer is not limited as long as the effect of the present invention is achieved, and may be determined appropriately. The positive electrode active material may be a prussian sodium salt, a sodium salt of a multi-component layered oxide, a manganic acid sodium salt, or a polyanionic sodium salt including sodium ferric sulfate, sodium ferric pyrophosphate, and sodium vanadium phosphate.
The positive electrode generally has a current collector, and as the positive current collector, a foil of stainless steel, copper, aluminum, nickel, or carbon can be used, with aluminum foil being preferred.
The material of the separator corresponding to the sodium ion battery is not particularly limited, and various separators generally used for lithium ion batteries, sodium ion secondary batteries, and capacitors can be used, and specific separators can be olefin separators such as polyethylene and polypropylene; polyimide PI and other high-temperature diaphragms; paper fiber or glass fiber woven high temperature membranes, with paper membranes being preferred.
The electrolyte material for the sodium ion battery is not particularly limited, and various electrolyte solvents generally used for lithium ion batteries and capacitors can be used, and the electrolyte sodium salt material can be at least one of sodium perchlorate, sodium hexafluorophosphate, sodium bifluorosulfonimide, sodium bistrifluoromethanesulfonimide, sodium trifluoromethanesulfonate, sodium tetrafluoroborate, sodium difluorophosphate, sodium acetate, and sodium tetraphenylborate. The electrolyte solvent can be: fluorinated carbonates, such as 3,3, 3-trifluoropropyl carbonate, fluoroethylene carbonate, methyl 2, 2-trifluoroethyl carbonate; 1, 3-dioxolan-2-one, 4- [2, 3-tetrafluoro-2- (trifluoromethyl) propyl ], or at least one of ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl acetate, ethyl propionate, ethyl acetate, or diethyl ether, ethylene glycol dimethyl ether, 1, 3-dioxolane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, methyl tert-butyl ether, or hydrofluoroether, fluoroether D2, preferably ether solvent or fluoroether, fluorinated carbonate solvent, the electrolyte concentration is 0.1-5mol.
Example 1:
all the components, percentages and ratios are based on weight, the N/P ratio of the battery is set to be 0.4/1, the battery capacity is 400mAh, and the sodium ion preparation process of the embodiment is as follows:
A. preparing a negative pole piece and preparing negative pole slurry: respectively setting a negative hard carbon material (full battery gram capacity 210mAh-280 mAh) with the model of CNY5, conductive carbon black, a binder SBR and a thickening agent CMC as 91.5% to 4.5% by mass ratio; 2.5 percent to 1.5 percent, uniformly compounding the components in deionized water to prepare negative electrode slurry, coating the negative electrode slurry on the surface of a carbon-coated aluminum foil with the thickness of 9um according to the unit area weight requirement of a negative electrode active material by using a transfer coater, drying, and coating a pole piece by using a roller press at the ratio of 0.9g/cm 3 The designed compacted density is subjected to roll-in treatment to prepare the final negative pole piece, as shown in the attached figures 1 and 2, the obtained pole piece has the advantages of surface density, compacted density, thickness, true density of each solid matter and porosity.
B. Manufacturing a positive pole piece: the positive active material layer oxide (full battery gram capacity 65mAh-100 mAh), the binder fluorine-containing PVDF and 1:2, carbon nano tube CNT and conductive carbon black are dissolved and uniformly mixed in NMP according to the mass ratio of 94.5 percent to 2.5 percent to 1.0 percent to 2.0 percent to prepare anode slurry, the anode slurry is coated on the surface of an aluminum foil with the thickness of 9um according to the mass requirement of the anode active material per unit area by utilizing a coating machine and dried, and then a coating pole piece is coated by a roller press at the ratio of 2.7-3.2g/cm 3 The final positive pole piece shown in the attached figures 3 and 4 is prepared by performing roll-in treatment on the designed compaction density.
C. Preparing an electrolyte: sodium hexafluorophosphate with the concentration of 1mol/L is dissolved in DME solvent to obtain the electrolyte.
D. Assembling a full battery: cutting the positive pole piece, the negative pole piece and the isolating membrane into corresponding sizes, winding the cut positive pole piece, the negative pole piece and the isolating membrane into dry cells by a winding machine, and then performing welding, aluminum plastic film packaging, high-temperature baking, liquid injection, formation, air exhaust, secondary packaging, formation and capacity grading process flow to prepare the 400mAh cylindrical soft package sodium ion composite battery.
The amount of electrolyte solution injected was set to 2.7 g.
Comparative example 1:
all the components, percentages and ratios are based on weight, the N/P ratio of the battery is 1.1/1, the battery capacity is 300mAh, and the sodium ion preparation process of the comparative example is as follows:
A. the preparation of the negative pole piece and the preparation of the negative pole slurry are the same as those of the negative pole piece in example 1, and the parameters of the coating thickness, the surface density, the compaction density, the true density and the porosity of each solid matter and the length and the width of the negative pole piece are adjusted according to the N/P ratio of 1.1/1, as shown in the attached figures 5 and 6.
B. Manufacturing a positive pole piece: dissolving a positive active material layer oxide, a binder fluorine-containing PVDF, a fluorine-free PAN mixture and carbon nano tube CNT, wherein conductive carbon black is dissolved in NMP according to the mass ratio of 94.5 to 2.5 to 1.0 to 2.0, dispersing and uniformly mixing to prepare positive slurry, coating the positive slurry on the surface of an aluminum foil with the thickness of 9 mu m according to the mass requirement of the positive active material per unit area by using a coating machine, drying, and coating a pole piece by using a roller press at the ratio of 2.7-3.5mg/mm 3 The final positive electrode sheet shown in the attached figures 7 and 8 is prepared by performing roll-in treatment on the designed compaction density.
C. Preparing an electrolyte: sodium hexafluorophosphate with the concentration of L mol/L is dissolved in DME solvent to obtain electrolyte.
D. Assembling a full battery: cutting the positive pole piece, the negative pole piece and the isolating membrane into corresponding sizes, winding the cut positive pole piece, the negative pole piece and the isolating membrane into dry cells by a winding machine, and then performing welding, aluminum plastic film packaging, high-temperature baking, liquid injection, formation, air exhaust, secondary packaging, formation and capacity grading process flow to prepare the 300mAh cylindrical soft package sodium ion composite battery.
The amount of electrolyte solution injected was set to 2.7 g.
Example 2:
example two, different from example one, the positive electrode active material was adjusted to be prussian white, and 3% by weight of the prussian white was replaced with sodium acetate (sodium oxalate), that is, the active material composition by weight was 97% prussian white +3% by weight of sodium acetate (sodium oxalate). The preparation of other negative pole pieces, electrolyte and the like is kept unchanged from the same embodiment, and the method specifically comprises the steps of uniformly compounding a positive active material Prussian white, sodium acetate, a binder SBR, a thickening agent CMC and conductive carbon black (Super-P) in a mass ratio of 93.12%:2.88%:2%:1%:4% in de-ionized water with oxygen removal to prepare positive slurry, wherein the sodium acetate is dissolved in the de-ionized water (the sodium acetate is horizontally dispersed in the positive slurry in a molecular level to obtain the best dispersion effect), coating the surface of an aluminum foil with the thickness of 9 mu m according to the unit area mass requirement of the positive active material by using a transfer coater, drying, uniformly separating out particles with the size smaller than nano level in the gap between the conductive agent of the positive pole piece and the Prussian white through a roller press, and performing roller press treatment on the coated pole piece at the designed compaction density of 1-1.5mg/mm < 3 to prepare the final positive pole piece. The battery prepared in the second embodiment has the charging voltage of 4.1V for the first time, sodium ions of sodium acetate are transferred to the negative electrode end and embedded into the negative electrode plate in the formation and charging process, and simultaneously carbon dioxide gas is generated and is pumped out of the battery in the vacuum pumping and packaging process of the battery or the implementation process of the negative pressure formation process, only sodium atoms are left in the battery, so that the first efficiency of the battery is improved by 3%, the weight of the battery is reduced, the battery capacity is kept the same as that of the first embodiment, and the battery cost is reduced by more than 1% (because the cost of the sodium acetate is only half of that of the positive active material).
The second embodiment shows that: by dissolving sodium acetate in deionized water (sodium acetate is dispersed in the anode slurry at a molecular level to obtain the best dispersion effect), the first efficiency of the battery is improved, the weight of the battery is reduced, the capacity of the battery is kept the same, and the cost of the battery is reduced (because the cost of sodium acetate is only half of that of the anode active material)
The performance data of example 1 and comparative example 1 were compared:
according to the surface density value, the active material content and the gram capacity value of the active material of the positive and negative pole pieces prepared in the embodiment 1, the N/P ratio of the battery in the embodiment 1 is 0.4/1, and the actual tested battery capacity is 402.0mAhWherein the design capacity of the positive active material is 465.2mAh, the first efficiency is 86.41 percent, the porosity of the negative pole piece is 35.53 percent by using an n-butanol method, and the total volume of the pores in the negative pole piece is V-Vi =0.81-0.522=0.288cm by multiplying the porosity of the negative pole piece by the volume of the negative pole piece 3 According to the theoretical density of sodium metal of 0.97g/cm 3 And obtaining the weight of sodium metal particles which can be stored in the pores in the negative pole piece as follows: 0.288cm3 x 0.97g/cm 3 =0.279g, corresponding to a gram capacity of 1166mAh/g of sodium metal, the maximum capacity of the sodium metal particles that can be stored in the pores inside the negative electrode sheet is: 0.279g 1166mAh/g =325.7mAh.
According to the surface density value, the active material content and the gram capacity value of the active material of the positive and negative pole pieces prepared in the comparative example 1, the N/P ratio of the battery in the comparative example 1 is 1.1/1, the actual test battery capacity is 323.2mAh, the designed capacity of the positive active material is 371.49mAh, and the first efficiency is 87%.
As can be seen by comparing example 1 with comparative example 1: the battery capacity of comparative example 1 is 80mAh less than that of example 1, that is, the battery capacity of comparative example 1 is only 323.2/402=80.39% of example 1, the volumetric specific energy density of example 1 is more than 19.61% higher than that of comparative example 1, and comparative example 1 is a production method of a general sodium-ion battery, which shows that the sodium metal particles and the sodium metal cluster/hard carbon alloy composite sodium battery of the present invention have an improved volumetric specific energy density compared to the conventional sodium-ion battery.
The cell specific energy density of example 1 was 0.402ah × 2.9v/13.6g =85.72wh/kg, and the cell specific energy density of comparative example 1 was 0.323ah × 2.94v/12.44g =76.33wh/kg, and it can be seen that the cell specific energy density of example 1 was 85.72Wh/kg/76.33Wh/kg =1.123, which is higher than that of comparative example 1, and was 12% or more, which also indicates that the sodium cell in which the sodium metal particles and the sodium metal clusters/hard carbon alloy are composited has an improved specific energy density by weight as compared with the conventional sodium ion cell.
As can be seen by comparing example 1 with comparative example 1: the battery of example 1, with an N/P ratio of less than 1, actually 0.4, was disassembled after full charging, and the cathode sheet size anatomical interface was observed using electron microscopy EDS to observe that sodium metal particles were filled in the pores of the sheet, whereas for comparative example 1, with an N/P ratio of greater than 1, actually 1.1, the battery after full charging was disassembled, and the cathode thickness anatomical interface was observed using electron microscopy EDS without observing sodium metal particles.
The internal resistance of the battery of example 1 is 55 milliohms, the cycle life test curve is shown in fig. 9, the charging and discharging voltage is set to be 3.45V-1.5V, the charging and discharging current is 1.5C, i.e. 600mA, the charging and discharging cycle is carried out for 300 times, the corresponding battery capacity and average voltage value when the battery is discharged to 1.5V from 3.45V after the first charging and discharging and 300 weeks of the charging and discharging cycle are recorded, the capacity retention ratio is more than 90%, the initial average voltage value is 2.91V, and the capacity retention ratio calculation method is as follows: the 300 week battery discharge capacity value is divided by the percentage of the initial discharge capacity value of the battery.
In summary, the present invention controls the N/P ratio of the positive electrode and the negative electrode to be less than 1, that is, the capacity ratio of the positive electrode plate to the negative electrode plate is less than 1, and the specific N/P ratio is: 0.99-0.1, namely the designed capacity of the negative pole piece is smaller than the capacity of the positive pole piece, so that part of sodium ions are embedded into the interlayer spacing and the defects of the hard carbon negative pole in the charging process of the battery, and because the capacity of the negative pole piece is smaller than the capacity of the positive pole piece, the molecular structure of the negative active material has insufficient space for accommodating all the sodium ions from the positive pole, so that part of the sodium ions of the positive pole can be separated out in the pores of the negative pole piece in a sodium metal mode in the charging process and exist in the pores of the negative pole piece in a granular solid sodium metal mode, and after the charging is finished, the negative end becomes the negative pole piece of the composite sodium battery of the sodium ion/hard carbon alloy and the granular sodium metal, and the composite sodium battery of the hard carbon type sodium ion battery and the granular sodium metal battery is formed.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "upper", "lower", "inner", "outer", "front", "rear", "both ends", "one end", "the other end", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless explicitly stated or limited otherwise, the terms "mounted," "disposed," "connected," and the like are to be construed broadly, such as "connected," which may be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in a specific case to those of ordinary skill in the art.
Claims (10)
1. The utility model provides a sodium ion battery, includes positive pole piece, negative pole piece, its characterized in that: by controlling the N/P ratio of the capacity of the positive pole piece and the capacity of the negative pole piece, the designed value of the capacity of the negative pole piece is smaller than the capacity of the positive pole piece, so that a part of sodium ions are firstly embedded into active substances of the negative pole piece in the charging process of the battery, and because the designed capacity of the negative pole piece is smaller than the capacity of the positive pole piece, the active substances of the negative pole piece do not have enough space to accommodate the sodium ions from the positive pole piece, the sodium ions are separated out in the pores of the negative pole piece in a sodium metal particle mode in the continuous charging process, and exist in the pores of the negative pole piece in a granular solid sodium metal mode, and the negative pole end becomes an alloy pole piece formed by compounding the sodium ions, sodium metal clusters, granular solid sodium metal and hard carbon negative pole, the obtained sodium ion battery is a composite sodium battery of a sodium ion/sodium metal cluster-hard carbon alloy battery and a granular solid sodium metal battery, the battery can be used as a secondary rechargeable sodium ion battery and a primary sodium metal battery, the rated voltage is 1.5-3.5V, the battery can be used for replacing a lithium metal primary battery with high cost, and the battery also can be used as an electrochemical device of the composite sodium battery of the hard carbon type sodium ion battery and the granular sodium metal battery.
2. The sodium-ion battery of claim 1, wherein the negative electrode material is a hard carbon material or other sodium intercalation material, the sodium intercalation material is one or more of titanium-based layered oxide, tin alloy, phosphide or phosphorus-carbon, pre-sodium phosphorus-carbon material, the phosphorus-carbon material is a nanoparticle phosphorus and carbon-coated composite, and the phosphide is Sn 3 P 4 SbP, or its pre-sodiated phosphocarbon material.
3. The sodium-ion battery according to claim 1, wherein the positive electrode material is one of a sodium salt of a multi-component layered oxide, prussian white, sodium manganate, and a polyanionic sodium salt, and the polyanionic sodium salt is one of a phosphate, a sulfate sodium compound (such as ferric sodium pyrophosphate, vanadium sodium phosphate, ferric sodium sulfate, and the like).
4. The method of claim 1, wherein the step of preparing comprises:
the method comprises the following steps: preparation of deoxygenated water: continuously injecting nitrogen into deionized water for more than one hour to remove oxygen in the water, or heating the deionized water to 100 ℃ and vacuumizing and stirring to remove the oxygen in the water, or using broken iron pins to coexist with the water for more than 24 hours to remove the oxygen in the water to obtain deoxygenated water;
step two: preparing slurry of the Prussian white positive electrode and a positive electrode plate: preparing anode slurry by using prepared deoxygenated water, stirring under vacuum pumping or under the protection of inert gas, vacuumizing and drying the prepared pole piece for at least 4 hours at the temperature higher than 150 ℃ to remove crystal water of active substances in the anode piece or vacuumizing and drying the prepared battery cell for at least 4 hours at the temperature higher than 150 ℃ before electrolyte injection to remove crystal water of the active substances in the anode piece to obtain an anode active material layered oxide, dissolving and uniformly mixing the anode active material layered oxide, a binder and a conductive agent in NMP according to a certain mass ratio, dispersing, preparing the anode slurry, coating the anode slurry on a current collector, drying, and rolling and forming.
Step three: adding a conductive agent, an adhesive and a solvent into the negative electrode pole piece to prepare negative slurry, coating the negative slurry on a current collector, drying and rolling for forming;
step four: preparing an electrolyte: the electrolyte is dissolved in an electrolyte solvent to obtain an electrolyte.
Step five: assembling a full battery: cutting the positive pole piece, the negative pole piece and the diaphragm into corresponding sizes, winding the cut positive pole piece, the negative pole piece and the diaphragm into dry cells by a winding machine, and then performing welding, aluminum plastic film packaging, high-temperature baking, liquid injection, formation, air exhaust, secondary packaging, formation and capacity grading process flow to prepare the cylindrical soft package sodium ion composite battery.
5. The method according to claim 4, wherein the current collectors of the positive and negative plates are at least one of a metal foil, a foam current collector, a metal mesh current collector, a carbon felt current collector, a carbon cloth current collector and a carbon paper current collector.
6. The method as claimed in claim 4, wherein the conductive agent comprises at least one of conductive carbon black, graphite, carbon fiber, single-walled carbon nanotube, multi-walled carbon nanotube, graphene, and fullerene.
7. The method for preparing the sodium-ion battery according to claim 4, wherein the compaction density of the negative pole piece is 0.5-1.8, the internal porosity of the pole piece is 1-99%, and the thickness of the active material-containing coating of the negative pole piece is more than 3 microns. The shape of the sodium metal particles is similar to the shape of the pores in the pole piece, and is spherical, elliptical, tadpole-shaped, and the like.
8. The method according to claim 4, wherein the separator substrate is an olefin, the olefin is polyethylene, polypropylene or polyimide PI high-temperature separator, or a paper fiber or glass fiber woven high-temperature separator, at least one surface of the separator substrate is coated with a surface treatment layer, and the surface treatment layer is a polymer layer, an inorganic layer or a layer formed by a composite polymer and an inorganic substance.
9. The method according to claim 4, wherein the electrolyte is at least one selected from sodium perchlorate, sodium hexafluorophosphate, sodium difluorosulfonimide, sodium bistrifluoromethane sulfonimide, sodium trifluoromethanesulfonate, sodium tetrafluoroborate, sodium difluorophosphate, sodium tetraphenylborate, and sodium chloride.
10. The method according to claim 4, wherein the electrolyte solvent is a fluorinated carbonate, the fluorinated carbonate is at least one of 3, 3-trifluoropropyl carbonate, fluoroethylene carbonate, methyl 2, 2-trifluoroethyl carbonate, 1, 3-dioxolan-2-one, 4- [2, 3-tetrafluoro-2- (trifluoromethyl) propyl ], ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, methylethyl carbonate, propylene carbonate, methyl acetate, ethyl propionate, fluoroethylene carbonate, or diethyl ether, ethylene glycol dimethyl ether, 1, 3-dioxolane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, methyl tert-butyl ether, hydrofluoroether, and fluoroether D2, preferably an ether solvent or a fluoroether or a fluorinated carbonate solvent, and the electrolyte concentration is 0.1 to 5mol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115832222A (en) * | 2022-12-29 | 2023-03-21 | 楚能新能源股份有限公司 | Flexible sodium-ion battery cathode, preparation method thereof and flexible sodium-ion battery |
| CN117199502A (en) * | 2023-11-06 | 2023-12-08 | 中自环保科技股份有限公司 | Preparation method of sodium ion battery |
| CN117276472A (en) * | 2023-11-21 | 2023-12-22 | 江苏中兴派能电池有限公司 | Positive pole piece of sodium ion battery, preparation method of positive pole piece and sodium ion battery |
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2022
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115832222A (en) * | 2022-12-29 | 2023-03-21 | 楚能新能源股份有限公司 | Flexible sodium-ion battery cathode, preparation method thereof and flexible sodium-ion battery |
| CN117199502A (en) * | 2023-11-06 | 2023-12-08 | 中自环保科技股份有限公司 | Preparation method of sodium ion battery |
| CN117199502B (en) * | 2023-11-06 | 2024-01-02 | 中自环保科技股份有限公司 | Preparation method of sodium ion battery |
| CN117276472A (en) * | 2023-11-21 | 2023-12-22 | 江苏中兴派能电池有限公司 | Positive pole piece of sodium ion battery, preparation method of positive pole piece and sodium ion battery |
| CN117276472B (en) * | 2023-11-21 | 2024-01-30 | 江苏中兴派能电池有限公司 | Positive pole piece of sodium ion battery, preparation method of positive pole piece and sodium ion battery |
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