CN111348687B - Crystal material, preparation method and application thereof, sodium ion battery positive electrode material, sodium ion battery and equipment - Google Patents

Crystal material, preparation method and application thereof, sodium ion battery positive electrode material, sodium ion battery and equipment Download PDF

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CN111348687B
CN111348687B CN201811561761.9A CN201811561761A CN111348687B CN 111348687 B CN111348687 B CN 111348687B CN 201811561761 A CN201811561761 A CN 201811561761A CN 111348687 B CN111348687 B CN 111348687B
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唐永炳
姚文娇
宋天一
吴南中
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Shenzhen Institute of Advanced Technology of CAS
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Abstract

The invention discloses a crystal material, a preparation method and application thereof, a sodium ion battery anode material, a sodium ion battery and equipment, and relates to the technical field of sodium ion batteries. The chemical formula of the crystal material is Na 2 M(C 2 O 4 )X·nH 2 O, wherein M is at least one positive divalent metal, X is a negative divalent anionic group, and X is not (C) 2 O 4 ) N is more than or equal to 0 and less than or equal to 12. The crystal material belongs to a hexagonal system and has a three-dimensional framework structure, and sodium ions and water molecules do not participate in the framework. The crystal material has good charge-discharge specific capacity and higher oxidation-reduction potential, and can remarkably improve the structural stability of the positive active material. The invention alleviates the defects of complex preparation process, high cost, unsatisfactory stability and the like of the conventional sodium-ion battery anode material. The positive electrode material of the sodium-ion battery provided by the invention has the advantages of high sodium intercalation performance, high oxidation-reduction potential, good cycle stability and low cost.

Description

Crystal material, preparation method and application thereof, sodium ion battery positive electrode material, sodium ion battery and equipment
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a crystal material, a preparation method and application thereof, a sodium ion battery positive electrode material, a sodium ion battery and equipment.
Background
The secondary battery is also called a rechargeable battery, and is a battery that can be repeatedly charged and discharged and recycled. Lithium ion batteries are widely applied to secondary batteries, have the advantages of high energy density and long service life, and are widely applied to the field of energy storage, but the natural abundance of lithium is low and is not uniformly distributed, so that the cost of the lithium ion batteries is increasingly increased. Sodium is located right below lithium in the periodic table of elements, has chemical properties similar to those of lithium, and has abundant reserves in the earth crust, and the abundance is about 1000 times of that of the lithium, so that the sodium-ion battery is expected to make up for the defects of the lithium-ion battery and becomes a new generation of high-performance and low-cost energy storage technology. The working principle of the sodium ion battery is similar to that of the lithium ion battery, and the storage and release of energy are realized by redox reactions of sodium ions on positive and negative electrodes. The core component of the sodium ion battery comprises a positive electrode, a negative electrode and an electrolyte. During charging, sodium ions are removed from the positive active material and are embedded into the negative active material; during discharge, sodium ions are extracted from the negative electrode active material and inserted into the positive electrode active material. In order to avoid the precipitation of metal sodium at the negative electrode, the designed capacity of the negative electrode of the sodium-ion battery is higher than that of the positive electrode, so that the capacity of the sodium-ion battery is determined by the positive electrode material. In addition, the voltage of the sodium ion battery is the potential difference between the anode material and the cathode material, and the higher the oxidation-reduction potential is, the more favorable the anode material is for obtaining the high voltage of the sodium ion battery. The structural stability of the positive electrode material is a major bottleneck in the development of the sodium ion battery at present.
The positive electrode material for sodium ion batteries can be roughly classified into a layered oxide, a polyanion compound, and an organic positive electrode. At the present stage, the types of the positive electrode materials of the sodium-ion battery are limited, the electrochemical performance is not ideal enough, and the preparation process is complex. The theoretical specific capacity of the layered oxide positive electrode material is higher, but irreversible oxygen release is easily triggered by high voltage, so that the battery fails. The organic positive electrode material has the problems of low working voltage and poor thermal stability. Compared with the prior art, the polyanionic compound has a stable structure, and the polyanionic group can adjust the electrochemical reaction potential of the material through induction, so the polyanionic compound has an excellent application prospect. However, in the current stage, researches on polyanionic positive electrode materials of sodium-ion batteries are few, and the polyanionic positive electrode materials are mainly concentrated on phosphate and sulfate systems, so that the preparation process is complex, the cost is high, and the performance is not ideal.
In view of the above, the present invention is particularly proposed to solve at least one of the above technical problems.
Disclosure of Invention
The first object of the present invention is to provide a crystalline material which belongs to the heteroisomorphic, hexagonal system, has a microscopically three-dimensional framework structure, wherein sodium ions and water molecules do not participate in the formation of the framework, and the crystal structure has abundant pore passages for the migration of the sodium ions. The crystal material can be used as a positive active material of a sodium ion battery, so that the sodium insertion performance of the positive active material containing the crystal material is greatly improved, and the oxidation-reduction potential and the structural stability of the positive active material are improved.
The second purpose of the invention is to provide a preparation method of the crystal material, the preparation method adopts a solvent to thermally synthesize the crystal, the process is simple, the cost is low, and the preparation method is suitable for industrial production.
The third purpose of the invention is to provide the application of the crystal material or the crystal material prepared by the preparation method of the crystal material in preparing the positive electrode active material.
The fourth purpose of the invention is to provide a positive electrode material of a sodium-ion battery, which comprises the crystal material or the crystal material prepared by the preparation method of the crystal material.
A fifth object of the present invention is to provide a sodium ion battery including the above-described positive electrode material for a sodium ion battery, which has the same advantages as the above-described crystal material or positive electrode active material for a sodium ion battery.
A sixth object of the invention is to provide an apparatus comprising a sodium-ion battery.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the present invention provides a crystalline material having the formula Na 2 M(C 2 O 4 )X·nH 2 O, wherein M is at least one positive divalent metal, X is a negative divalent anionic group, and X is not (C) 2 O 4 )，0≤n≤12；
Further, on the basis of the technical scheme provided by the invention, M is at least one positive divalent transition metal;
preferably, the M is at least one of Ti, V, cr, mn, co, ni, cu or Zn, or a combination of at least one of the foregoing metals and Fe;
preferably, said X is (SO) 4 )、(SeO 4 )、(PO 3 F)、(HPO4)、(HAsO 4 )、(MoO 4 )、 (WO 4 )、(S 2 O 7 ) Or (Se) 2 O 7 ) N is more than or equal to 0 and less than or equal to 6;
preferably, the crystalline material has the chemical formula Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O、 Na 2 Ni(C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Mn(C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Cu(C 2 O 4 )(SO 4 )·2H 2 O、 Na 2 Fe 0.5 Mn 0.5 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Fe 0.75 Mn 0.25 (C 2 O 4 )(SO 4 )·2H 2 O、 Na 2 Fe 0.9 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Fe 0.9 Ti 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、 Na 2 Fe 0.9 V 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Fe 0.9 Zn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、 Na 2 Fe 0.9 Cu 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Ti 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、 Na 2 Ni 0.6 Mn 0.2 Co 0.2 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 V 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、 Na 2 V 0.2 Fe 0.7 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Co(C 2 O 4 )(SO 4 )·6H 2 O、 Na 2 Co(C 2 O 4 )(SeO 4 )·2H 2 O、Na 2 Fe(C 2 O 4 )(SeO 4 )·4H 2 O、 Na 2 Fe(C 2 O 4 )(WO 4 )·6H 2 O、Na 2 Fe(C 2 O 4 )(S 2 O 7 )·2H 2 O or Na 2 Fe(C 2 O 4 )(HPO 4 )·2H 2 And O is one of the compounds.
Further, on the basis of the technical scheme provided by the invention, the chemical formula of the crystal material is Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O belongs to a hexagonal system, the space group is P-63m, the water loss temperature is 180 ℃, the decomposition temperature is 300 ℃, and the unit cell parameter is
Figure BDA0001913438660000031
Figure BDA0001913438660000032
α＝β＝90°，γ＝120°，
Figure BDA0001913438660000033
Z＝1；
Preferably, the crystalline material has the chemical formula Na 2 Ni(C 2 O 4 )(SO 4 )·2H 2 O, belonging to a hexagonal system, the space group is P-63m, the water loss temperature is 180 ℃, and the decomposition temperature is 310 ℃; unit cell parameter of
Figure BDA0001913438660000034
α＝β＝90°，γ＝120°，
Figure BDA0001913438660000035
Z＝1。
In a second aspect, the present invention provides a method for preparing a crystalline material, comprising the steps of: uniformly mixing a sodium source, an M source, an oxalate source, an X source and a solvent, and then carrying out a solvothermal reaction to obtain a crystal material;
preferably, the molar ratio of the sodium source, the M source, the oxalate source and the X source is (2-8) to 1 (1-8) to (2-8);
preferably, the sodium source comprises at least one of a sodium-containing oxide, base or salt;
preferably, the M source comprises at least one of an oxide, acid, base, salt or simple substance M containing M;
preferably, the oxalate source comprises at least one of an oxalate-containing acid or salt;
preferably, the source of X comprises at least one of an acid or salt comprising X;
preferably, the solvent is at least one of water, alcohols, ketones, or pyridines, preferably water.
Further, on the basis of the technical scheme provided by the invention, the temperature of the solvothermal reaction is 100-300 ℃, and the time is 4-100h.
Preferably, the temperature of the solvothermal reaction is 180-220 ℃ and the time is 48-72h.
In a third aspect, the present invention provides an application of the above crystalline material, or a crystalline material prepared by the above preparation method of the crystalline material, in preparation of a positive electrode active material.
In a fourth aspect, the invention provides a sodium ion battery cathode material, which comprises the above crystal material, or a crystal material prepared by the above preparation method of the crystal material.
Further, on the basis of the technical scheme provided by the invention, the battery comprises a positive active material, a positive conductive agent and a positive binder; the weight ratio of the positive active material, the positive conductive agent and the positive binder is (60-90): 5-30): 3-10; the positive active material is the crystalline material;
further, on the basis of the technical scheme provided by the invention, the positive electrode conductive agent comprises at least one of conductive carbon black, conductive carbon spheres, conductive graphite, conductive carbon fibers, carbon nanotubes, graphene or reduced graphene oxide;
further, on the basis of the technical scheme provided by the invention, the positive electrode binder comprises at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, styrene-butadiene rubber or polyolefin.
In a fifth aspect, the invention provides a sodium-ion battery, which comprises the positive electrode material of the sodium-ion battery.
In a sixth aspect, the invention provides an apparatus comprising the sodium ion battery described above.
Compared with the prior art, the invention has the following beneficial effects:
(1) The chemical formula of the crystal material provided by the invention is Na 2 M(C 2 O 4 )X·nH 2 O (wherein M is at least one positive divalent metal ion, X is a negative divalent anion group, n is more than or equal to 0 and less than or equal to 12), belongs to a heterogeneous isomorphic, hexagonal crystal system and has a microscopic three-dimensional framework structure, wherein M, C 2 O 4 And X together form a framework, and sodium ions and water molecules do not participate in the formation of the framework. The three-dimensional framework structure is provided with abundant lattice channels for sodium ion migration, and an effective path for the deintercalation and intercalation of sodium ions is provided. The crystal material can be used as a positive active material of a sodium ion battery, so that the sodium insertion performance of the positive active material containing the crystal material is greatly improved, and the oxidation-reduction potential and the structural stability of the positive active material are improved.
(2) The positive electrode material of the sodium ion battery provided by the invention comprises the positive electrode active material prepared from the crystal material, and has the advantages of high sodium intercalation performance, high oxidation-reduction potential, good cycle stability and low cost.
(3) The preparation method of the anode active material provided by the invention adopts a method of solvothermal synthesis of crystals, has simple process and low cost, and is suitable for industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 shows a crystal material Na provided by the present invention 2 M(C 2 O 4 )(SO 4 )·nH 2 A structural schematic diagram of O;
FIG. 2 shows the crystalline material Na provided in example 1 of the present invention 2 Co(C 2 O 4 )(SO 4 )·2H 2 A crystal photograph of O;
FIG. 3 shows a crystalline material Na provided in example 1 of the present invention 2 Co(C 2 O 4 )(SO 4 )·2H 2 A comparison graph of an XRD spectrogram and a theoretical spectrogram of the O;
FIG. 4 shows a crystal material Na provided in example 1 of the present invention 2 Co(C 2 O 4 )(SO 4 )·2H 2 Thermogravimetric analysis of O;
fig. 5 is a graph showing the cycle stability test of the sodium ion half cell of example 21 of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
In the present invention, all the embodiments and preferred methods mentioned herein can be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, the percentage (%) or parts means the mass percentage or parts by weight with respect to the composition, unless otherwise specified.
In the present invention, the components referred to or the preferred components thereof may be combined with each other to form a novel embodiment, unless otherwise specified.
In the present invention, unless otherwise stated, 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, a numerical range of "6 to 22" indicates that all real numbers between "6 to 22" have been listed herein, and "6 to 22" is only a shorthand representation of the combination of these numbers.
The "ranges" disclosed herein may have one or more lower limits and one or more upper limits, respectively, in the form of lower limits and upper limits.
In the present invention, unless otherwise specified, the individual reactions or process steps may or may not be performed in sequence. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.
According to a first aspect of the present invention there is provided a crystalline material having the formula Na 2 M(C 2 O 4 )X·nH 2 O, wherein M is at least one positive divalent metal, X is a negative divalent anionic group, and X is not (C) 2 O 4 )，0≤n≤12。
The crystal material belongs to a heterogeneous isomorphism, is in a hexagonal prism shape or a tetragonal prism shape in a macroscopic view, and belongs to a hexagonal crystal system. The crystal material has a three-dimensional framework structure, wherein M and (C) 2 O 4 ) And X together form a skeleton, and Na ions and water molecules do not participate in the structure of the skeleton. Plane type [ M (C) comprising 3 molecules in unit cell 2 O 4 )]3 molecules of negative divalent X anion groups, 6 molecules of Na ions and a plurality of free water molecules; wherein the negative divalent X anion group is a bridging anion group.
Specifically, as shown in FIG. 1, na was confirmed by single crystal X-ray diffraction experiment 2 M(C 2 O 4 )(SO 4 )·nH 2 O crystalThe schematic diagram of the unit cell microstructure of the material comprises: every four oxygen atoms and every two carbon atoms form a planar oxalate group; each M metal atom is connected to oxalate through oxygen bridge bond to form planar [ M (C) 2 O 4 )]A two-dimensional mesh plane; the sulfate anion groups being linked to adjacent [ M (C) 2 O 4 )]Two-dimensional mesh planes, thereby forming a three-dimensional skeleton structure; the Na ions and water molecules are stabilized in the voids of the framework by electrostatic interaction and hydrogen bonding, respectively. Wherein the carbon-oxygen bond length is
Figure BDA0001913438660000071
Carbon-carbon bond length of
Figure BDA0001913438660000072
The metal-oxygen bond length is
Figure BDA0001913438660000073
The atoms nearest to sodium have 5-7 kinds and bond length of
Figure BDA0001913438660000074
M is at least one positive divalent metal, and forms an extended two-dimensional reticular plane by combining with oxalate, the type of M is not limited, and M can be one or more positive divalent metal elements, and the structure of the crystal material can be unchanged.
X is a negative divalent anionic group, the type of X is not limited, and the valence can be negative divalent. The X anion group can ensure the electric neutrality principle of the whole configuration, and is beneficial to metal ions (such as Na) + ) The rapid conduction in the framework structure can also ensure the stability of the structure in the oxidation-reduction process.
The crystal water in the crystal material does not participate in the formation of the crystal structure, but the stability of the crystal structure is affected by the excessive amount of the crystal water. The number n of crystal water in the crystal material may be 0, 12, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
The microscopic three-dimensional framework structure of the crystal has abundant lattice channels for sodium ion migration, provides effective paths for the deintercalation and the intercalation of sodium ions, and provides more active sites for the sodium ions. The crystal material can be used as a positive active material of a sodium ion battery, so that the sodium insertion performance of the positive active material is greatly improved, and the oxidation-reduction potential and the structural stability of the positive active material are improved.
In a preferred embodiment, M is at least one positive divalent transition metal;
preferably, M is at least one of Ti, V, cr, mn, co, ni, cu or Zn, or a combination of at least one of the foregoing metals and Fe;
preferably X is (SO) 4 )、(SeO 4 )、(PO 3 F)、(HPO4)、(HAsO 4 )、(MoO 4 )、(WO 4 )、 (S 2 O 7 ) Or (Se) 2 O 7 ) N is more than or equal to 0 and less than or equal to 6.
In the case where M is two or more metals, the sum of the number of moles of each metal is the same as the number of moles of oxalate ions, and the molar ratio between the metal elements does not affect the structure of the crystal material.
Preferably, the metal M is selected from the group consisting of [ M (C) 2 O 4 )]The structure of the two-dimensional mesh plane is more stable, and richer sodium ion pore channels are provided; the preferred X species and the further preferred X are regular tetrahedral anionic groups, which can reduce the space occupation volume of the X anionic groups, provide more space for sodium ion channels and connect adjacent [ M (C) more stably 2 O 4 )]A two-dimensional mesh plane; the number of crystal water is preferably selected so as to significantly reduce the influence of crystal water on the crystal structure.
The chemical formula of the preferred crystalline material may be, but is not limited to, na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O、 Na 2 Ni(C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Mn(C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Cu(C 2 O 4 )(SO 4 )·2H 2 O、 Na 2 Fe 0.5 Mn 0.5 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Fe 0.75 Mn 0.25 (C 2 O 4 )(SO 4 )·2H 2 O、 Na 2 Fe 0.9 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Fe 0.9 Ti 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、 Na 2 Fe 0.9 V 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Fe 0.9 Zn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、 Na 2 Fe 0.9 Cu 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Ti 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、 Na 2 Ni 0.6 Mn 0.2 Co 0.2 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 V 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、 Na 2 V 0.2 Fe 0.7 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Co(C 2 O 4 )(SO 4 )·6H 2 O、 Na 2 Co(C 2 O 4 )(SeO 4 )·2H 2 O、Na 2 Fe(C 2 O 4 )(SeO 4 )·4H 2 O、 Na 2 Fe(C 2 O 4 )(WO 4 )·6H 2 O、Na 2 Fe(C 2 O 4 )(S 2 O 7 )·2H 2 O or Na 2 Fe(C 2 O 4 )(HPO 4 )·2H 2 And O is one of the compounds.
In the preferred crystalline materials, the linkage [ M (C) is selected as an anionic group of the tetrahedral type 2 O 4 )]The two-dimensional mesh plane bridge can ensure that the crystal material provides more abundant pore passages for sodium ion migration, provides more active sites for sodium ions, improves the sodium insertion performance of the crystal material and improves the sodium insertion performanceAnd (4) structural stability.
In a preferred embodiment, the crystalline material is of the formula Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O belongs to a hexagonal system, the space group is P-63m, the water loss temperature is 180 ℃, the decomposition temperature is 300 ℃, and the unit cell parameter is
Figure BDA0001913438660000091
Figure BDA0001913438660000092
α＝β＝90°，γ＝120°，
Figure BDA0001913438660000093
Z＝1。
FIG. 2 shows a crystal material Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 And O, the crystal material is microscopically hexagonal column-shaped.
FIG. 3 shows Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 And comparing the theoretical spectrum of the O crystal with the experimental XRD spectrum, wherein the theoretical spectrum is an X-ray diffraction spectrum deduced from the single crystal structure. As can be seen from FIG. 3, the peaks of the experimental spectrum and the theoretical spectrum are well matched, which indicates that the experimental sample has good crystallinity and high purity. In addition, the relative intensity of the diffraction peaks is slightly different from the theoretical spectrum due to Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 Due to the anisotropic growth habit of the O crystal material.
FIG. 4 shows Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 The thermogravimetric analysis diagram of the O crystal shows that when the substance is heated to 180 ℃, the weight loss reaches 11.03 percent, which corresponds to the loss of two crystal waters, as can be seen from FIG. 4; when heating was continued to 310 ℃ the total weight loss was about 31%, corresponding to Na 2 Co(C 2 O 4 )(SO 4 ) Decomposition of the compound into sodium sulfate and transition metal oxide Co 2 O 3 。
In a preferred embodiment, the crystalline material is solidifiedChemical formula is Na 2 Ni(C 2 O 4 )(SO 4 )·2H 2 O belongs to a hexagonal system, the space group is P-63m, the water loss temperature is 180 ℃, the decomposition temperature is 310 ℃, and the unit cell parameter is
Figure BDA0001913438660000094
Figure BDA0001913438660000095
α＝β＝90°，γ＝120°，
Figure BDA0001913438660000096
Z＝1。
According to a second aspect of the present invention, there is provided a method for preparing the above crystalline material, comprising the steps of: uniformly mixing a sodium source, an M source, an oxalate source, an X source and a solvent, and then carrying out a solvothermal reaction to obtain a crystal material;
the solvent is preferably water, that is, the solvothermal reaction is preferably a hydrothermal reaction to prepare the crystalline material, and the hydrothermal reaction refers to an effective method for performing inorganic synthesis and material treatment by heating (or self-raising vapor pressure) in a specified closed reactor (autoclave) by using an aqueous solution as a reaction system to create a relatively high-temperature and high-pressure reaction environment, so that substances which are usually insoluble or insoluble are dissolved, and recrystallizing. The crystal material obtained after the hydrothermal reaction can be seen by naked eyes and is in a hexagonal prism shape or a square column shape in a macroscopic view.
The order of adding the sodium source, the M source, the oxalate source, and the X source to the solvent may be changed arbitrarily, and the preferable order is to add the M source, the oxalate source, the sodium source, and the X source in this order.
In order to make the structure of the prepared crystal material better and shorten the preparation time, the mol ratio of the sodium source, the M source, the oxalate source and the X source is preferably (2-8) to 1 (1-8) to (2-8); the molar ratio of the sodium source, oxalate source and X source can be 2.
The sodium source comprises at least one of a sodium-containing oxide, base or salt; sodium sources include, but are not limited to, one or more of sodium carbonate, sodium acetate, sodium nitrite, sodium fluoroborate, sodium bromide, sodium sulfate, sodium oxalate, sodium persulfate, sodium hydroxide, sodium pyrosulfate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium metabisulfite, sodium pyrophosphate, sodium chromium sulfate, sodium hydrogen tartrate, sodium dichromate, sodium hydrogen phthalate, sodium hydrogen oxalate, sodium sulfite, sodium sorbate, sodium fluorosilicate, trisodium phosphate, sodium gluconate, or sodium oleate; preferably, the sodium source is one or more of sodium carbonate, sodium hydroxide or sodium sulfate; sodium sulfate is preferred.
The M source comprises at least one of an oxide, an acid, a base, a salt or a simple substance M containing M; preferably, M is at least one of Ti, V, cr, mn, fe, co, ni, cu, or Zn, or a combination of at least one of the foregoing metals with Fe. Specifically, the M source may be one or more of a titanium source, a vanadium source, a chromium source, a manganese source, an iron source, a cobalt source, a nickel source, a copper source, or a zinc source.
The titanium source includes, but is not limited to, one or more of elemental titanium, titanyl trioxide, titanium dioxide, titanium (III) sulfate, titanium (IV) sulfate, titanium phosphate, sodium fluorotitanate, hexafluorotitanic acid, tetrabutyl titanate, tetraethyl titanate, isopropyl titanate, titanium tetrachloride, titanium trichloride, titanium dihydride, ammonium fluorotitanate, titanium tetrafluoride, titanocene dichloride, or bis (acetylacetonate) isopropyl titanate, and hydrates thereof; preferably, the titanium source is one or more of titanium tetrafluoride, titanium (III) sulfate or titanium trichloride.
Vanadium sources include, but are not limited to, one or more of elemental vanadium, vanadium trioxide, vanadium dioxide, vanadium pentoxide, vanadium difluoride, vanadium trifluoride, vanadium tetrafluoride, vanadium pentafluoride, vanadium oxyfluoride, vanadium dichloride, vanadium trichloride, vanadium tetrachloride, vanadium oxychloride, vanadium dibromide, vanadium tribromide, vanadium tetrabromide, ammonium metavanadate, sodium orthovanadate, sodium metavanadate, vanadium acetylacetonate, vanadium oxoacetylacetonate, vanadium triisopropoxide, or vanadium tripropanolate oxide, and hydrates thereof; preferably, the vanadium source is one or more of vanadium dioxide, vanadium pentoxide or vanadium oxyfluoride.
Chromium sources include, but are not limited to, one or more of elemental chromium, chromium trioxide, chromium dioxide, chromium sesquioxide, chromium hydroxide, chromium sulfate, lithium chromite, potassium dichromate, sodium dichromate, chromium vanadium, chromium trifluoride, chromium dichloride, chromium trichloride, chromium bromide, chromium orthophosphate, chromium metaphosphate, chromium pyrophosphate, chromium acid phosphate, chromium basic phosphate, chromium phosphochlorate, chromium nitrate, chromium nitrite, chromium formate, cadmium acetate, chromium acetate or chromium oxalate, and hydrates thereof; preferably, the chromium source is one or more of chromium hydroxide, chromium dichloride or chromium trichloride.
Manganese sources include, but are not limited to, one or more of elemental manganese, manganese oxide, manganese dioxide, manganous manganic oxide, manganese (II) fluoride, manganese (III) fluoride, manganese (II) chloride, manganese (III) chloride, manganese bromide, manganese carbonate, manganese nitrate, manganese sulfate, manganese phosphate, manganese dihydrogen phosphate, manganese acetylacetonate, manganese formate, manganese (II) acetate, manganese (III) acetate, or manganese oxalate, and hydrates thereof; preferably, the manganese source is one or more of manganese acetate, manganese oxalate or manganese chloride.
Cobalt sources include, but are not limited to, one or more of elemental cobalt, cobalt monoxide, cobaltic oxide, cobalt (II) hydroxide, cobalt (III) hydroxide, cobalt (II) fluoride, cobalt (III) fluoride, cobalt (II) chloride, cobalt (III) chloride, cobalt bromide, cobalt nitrate, cobalt sulfate, cobalt carbonate, cobalt acetate, cobalt oxalate, cobalt hexa-amino chloride or cobalt acetylacetonate, and hydrates thereof; preferably the cobalt source is one or more of cobalt acetate, cobalt oxalate or cobalt chloride.
Nickel sources include, but are not limited to, one or more of elemental nickel, nickel oxide, nickelous oxide, nickel hydroxide, nickelous hydroxide, nickel fluoride, nickel chloride, nickel bromide, nickel nitrate, nickel carbonate, nickel sulfate, nickel acetate, nickel oxalate, nickel bis (hexafluoroethylacetone), nickel sulfamate, nickel hydroxycarbonate, nickel acetylacetonate dihydrate, nickel triflate, nickel benzenesulfonate, nickel acetylacetonate, or nickel fluoroborate, and hydrates thereof; preferably the nickel source is one or more of nickel oxalate, nickel chloride, nickel fluoride or nickel acetate.
Copper sources include, but are not limited to, one or more of elemental copper, cuprous oxide, cupric hydroxide, cupric fluoride, cupric chloride, cupric bromide, cupric carbonate, basic cupric carbonate, cupric nitrate, cupric sulfate, cupric acetate, cupric oxalate, cupric tartrate, cupric citrate, cupric fluoroborate, cupric acetylacetonate, or cupric gluconate, and hydrates thereof; preferably, the copper source is one or more of copper acetate, copper sulfate or copper chloride.
Zinc sources include, but are not limited to, one or more of elemental zinc, zinc oxide, zinc hydroxide, zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, zinc carbonate, zinc acetate, zinc oxalate, zinc citrate, zinc fluoroborate, zinc tartrate, zinc borate, zinc metaborate, zinc acetylacetonate, or zinc gluconate, and hydrates thereof; preferably, the zinc source is one or both of zinc sulfate and zinc chloride.
The iron source includes, but is not limited to, one or more of elementary iron, ferric oxide, ferroferric oxide, ferrous hydroxide, ferric hydroxide, ferrous fluoride, ferric fluoride, ferrous chloride, ferric chloride, ferrous bromide, ferric formate, ferrous acetate, ferrous nitrate, ferrous sulfate, ferric nitrate, ferric sulfate, ferric acetylacetonate, ferrous oxalate, ferric oxalate and hydrates thereof; preferably, the iron source is one or more of ferrous oxalate, ferrous chloride and hydrates thereof.
The oxalate source comprises at least one of an oxalate-containing acid or salt; oxalate sources include, but are not limited to, one or more of oxalic acid, sodium oxalate, sodium hydrogen oxalate, ammonium oxalate or diethyl oxalate and hydrates thereof; oxalic acid and its hydrates are preferred.
The source of X is a source of a negative divalent anionic group and may be, but is not limited to, at least one of an X-containing acid or salt. Preferably X is (SO) 4 )、(SeO 4 )、(PO 3 F)、(HPO4)、(HAsO 4 )、(MoO 4 )、 (WO 4 )、(S 2 O 7 ) Or (Se) 2 O 7 ) One of the anionic groups. Specifically, the X source may be one of a sulfate source, a selenate source, a fluorinated phosphate source, a monohydrogen arsenate source, a molybdate source, a tungstate source, a pyrosulfate source, or a pyroselenate source.
Sulfate sources include, but are not limited to, one or more of sulfuric anhydride, sulfuric acid solution, alkali metal sulfate, alkaline earth metal sulfate, ammonium bisulfate, or desired transition metal sulfate; one or both of sulfuric acid and sodium sulfate are preferred.
Selenate sources include, but are not limited to, one or more of selenate anhydride, selenate acid, alkali metal selenates, alkaline earth metal selenates, ammonium selenate, ammonium hydrogen selenate, or the desired transition metal selenates; one or two of selenate and sodium selenate are preferred.
Fluorinated phosphate sources include, but are not limited to, one or more of fluorinated phosphoric acid, fluorinated lithium phosphate, fluorinated sodium phosphate, fluorinated potassium phosphate, fluorinated ammonium phosphate, or fluorinated rubidium phosphate; one or both of fluorinated phosphoric acid and sodium phosphate are preferred.
Sources of monohydrogen phosphates include, but are not limited to, one or more of phosphoric acid anhydride, phosphoric acid, alkali metal monohydrogen phosphates, alkaline earth metal monohydrogen phosphates, or desired transition metal monohydrogen phosphates; one or both of sodium monohydrogen phosphate and transition metal phosphate are preferred.
The mono-hydrogen arsenate source includes, but is not limited to, one or more of arsenic anhydride, arsenate solution, alkali metal arsenate, alkaline earth metal arsenate, ammonium hydrogen arsenate or the desired transition metal arsenate; one or both of arsenic acid and sodium arsenate are preferred.
Molybdate sources include, but are not limited to, one or more of molybdenum trioxide, molybdic acid solution, alkali metal molybdate, alkaline earth metal molybdate, ammonium hydrogen molybdate, or the desired transition metal molybdate; one or both of molybdic acid and sodium molybdate are preferred.
Sources of tungstic acid include, but are not limited to, one or more of tungstic anhydride, tungstic acid solution, alkali metal tungstate, alkaline earth metal tungstate, ammonium hydrogen tungstate or the desired transition metal tungstate; one or both of tungstic acid and sodium tungstate are preferred.
The pyrosulfate source includes, but is not limited to, one or more of pyrosulfate anhydride, a pyrosulfate solution, an alkali metal pyrosulfate, an alkaline earth metal pyrosulfate, ammonium hydrogen pyrosulfate, or a desired transition metal pyrosulfate; one or both of pyrosulfuric acid and sodium pyrosulfate are preferable.
Jiao Xisuan sources include, but are not limited to, one or more of pyroselenic anhydride, jiao Xisuan solution, alkali metal pyroselenate, alkaline earth metal pyroselenate, ammonium pyroselenate, jiao Xi ammonium hydrogen acid, or desired transition metal pyroselenate; preferably Jiao Xisuan and sodium pyroselenate.
The hydrate of the compound providing the sodium source, the M source, the oxalate source, and the X anion source may be used as a raw material source for hydrothermal synthesis, and the hydrate does not affect the crystal structure obtained by the preparation.
The solvent is at least one of water, alcohols, ketones or pyridines; preferred solvents include, but are not limited to, one or more of water, methanol, ethanol, acetone, ethylene glycol or pyridine, preferably water.
In a preferred embodiment, the temperature of the solvothermal reaction is 100-300 ℃ for 4-100h; the temperature of the solvothermal reaction is preferably 180-220 ℃ and the time is 48-72h.
The temperature of the solvothermal reaction is typically, but not limited to, 100 ℃, 130 ℃, 150 ℃, 180 ℃, 200 ℃, 230 ℃, 270 ℃ or 300 ℃, for example; the solvothermal reaction time is typically, but not limited to, for example, 4h, 10h, 20h, 30h, 40h, 50h, 60h, 70h, 80h, 90h or 100h.
An exemplary method of making a crystalline material comprises the steps of:
(a) Weighing a sodium source, an M source, an oxalate source and an X anion source according to a certain proportion, adding the weighed raw materials into a reactor filled with a solvent, and uniformly mixing to obtain a mixed solution;
(b) Heating the mixed solution at 100-300 ℃ for 4-100h to obtain a primary product of a crystal material;
(c) And washing and drying the primary product of the crystal material to obtain the crystal material.
It should be noted that the order of charging the raw materials in step (a) is not particularly limited as long as a uniform mixed solution can be obtained after mixing.
The exemplary preparation method of the crystalline material defines the process parameters of the preparation process, clearly shows the sequence relation of each process step, and according to the exemplary preparation method, the preparation process time can be shortened, and the crystalline material with better purity can be obtained.
According to a third aspect of the present invention, there is provided a use of the above crystalline material for producing a positive electrode active material.
The crystal material has a microscopic three-dimensional framework structure, and the three-dimensional framework structure has abundant crystal lattice channels for sodium ion migration, provides effective diffusion paths for the deintercalation and intercalation of sodium ions, and provides more active sites for the sodium ions, so the crystal material can be used as a positive electrode active material of a sodium ion battery.
It should be noted that, since the crystalline material obtained by the above preparation method has large particles, a particle size of about 4 to 5mm and is visible to the naked eye, the positive electrode active material for a sodium ion battery needs to be used after being ground, and the ground particle size is preferably 100 to 2000nm. The particle size of the milled, and preferably ground, crystalline material may increase its contact area with the electrolyte, providing more active sites for sodium ions.
According to a fourth aspect of the present invention, there is provided a positive electrode material for a sodium ion battery, comprising a positive electrode active material, a positive electrode conductive agent and a positive electrode binder; the weight ratio of the positive active material, the positive conductive agent and the positive binder is (60-90): 5-30): 3-10; the positive electrode active material is the above-described crystalline material.
The weight ratio of the positive electrode active material, the positive electrode conductive agent, and the positive electrode binder is typically, but not limited to, 60.
The conductive agent is used for ensuring that the electrode has good conductive performance, a certain amount of conductive substances are usually added when the positive electrode is manufactured, and the effect of collecting micro-current is achieved among active substances and between the active substances and a current collector, so that the movement rate of electrons accelerated by the contact resistance of the electrode is reduced, and meanwhile, the migration rate of sodium ions in the electrode material can be effectively improved, and the charging and discharging efficiency of the electrode is improved. The positive electrode conductive agent can be, but is not limited to, conductive carbon black conductive carbon spheres, conductive graphite at least one of conductive carbon fibers, carbon nanotubes, graphene or reduced graphene oxide.
The binder can ensure that certain bonding strength exists between active material particles and between the active material particles and a current collector in the using process of the battery, is favorable for SEI film formation, and improves the cycle performance and the service life of the electrode. The positive electrode binder may be, but is not limited to, at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, styrene Butadiene Rubber (SBR), or polyolefin.
The weight ratio of the positive electrode active material, the positive electrode conductive agent and the positive electrode binder and the types of the used positive electrode conductive agent and the positive electrode binder are optimized, so that the positive electrode active material is favorably attached to the current collector, the charge and discharge efficiency of the positive electrode is improved, and the electrochemical performance of the prepared positive electrode material of the sodium-ion battery is better.
Using the above crystalline material Na 2 M(C 2 O 4 )X·nH 2 O (wherein M is a divalent positive metal, X is a divalent negative anionic group, and X is not (C) 2 O 4 ) And n is more than or equal to 0 and less than or equal to 12) is used as the positive active material of the positive material of the sodium-ion battery, so that the positive material of the sodium-ion battery has the same advantages as the crystal material and the positive active material, and has the advantages of high sodium intercalation performance, high oxidation-reduction potential, good cycle stability and low cost.
According to a fifth aspect of the present invention, there is provided a sodium-ion battery comprising the above-described positive electrode material for sodium-ion batteries.
The sodium ion battery may be in the form of, but is not limited to, a button cell, a flat cell, or a cylindrical cell.
The working principle of the sodium ion battery is similar to that of the lithium ion battery, and in order to avoid the precipitation of metal sodium on the negative electrode, the designed specific capacity of the negative electrode of the sodium ion battery is higher than that of the positive electrode, so that the capacity of the sodium ion battery is determined by the positive electrode material. The positive electrode active material or the positive electrode material of the sodium ion battery provided by the invention is used as the positive electrode, so that the sodium ion battery has the advantages of large battery capacity, good cycle stability and low cost.
In addition to the above-described sodium ion positive electrode material, the sodium ion battery includes a negative electrode material, a negative electrode current collector, a positive electrode current collector, an electrolyte, and a separator.
In a preferred embodiment, the negative electrode material comprises a negative electrode active material, a negative electrode conductive agent and a negative electrode binder, and the weight ratio of the negative electrode active material to the negative electrode conductive agent to the negative electrode binder is (60-90): (5-30): (3-10);
the negative active material may preferably be, but not limited to, at least one of a carbon material, a metal, an alloy, a sulfide, a nitride, an oxide, or a carbide.
Preferably, the negative electrode conductive agent can be, but is not limited to, at least one of conductive carbon black, conductive carbon spheres, conductive graphite, conductive carbon fibers, carbon nanotubes, graphene or reduced graphene oxide; the preferable negative electrode binder may be, but is not limited to, at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, styrene-butadiene rubber, or polyolefin.
Preferably, the materials of the negative electrode current collector and the positive electrode current collector respectively and independently comprise one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth or germanium, or an alloy of the above metals, or a composite of the above metals;
the negative electrode conductive agent, the negative electrode binder and the addition amount thereof are preferably selected, so that the negative electrode active material can be favorably attached to the negative electrode current collector, and the charge and discharge efficiency of the negative electrode is improved.
In a preferred embodiment, the electrolyte comprises an electrolyte and an electrolyte solvent; electrolyte is sodium salt.
The sodium salt is preferably present in the electrolyte at a molar concentration of 0.1 to 10mol/L, with typical but non-limiting examples being 0.1mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L or 10mol/L.
The sodium salt as the electrolyte is not particularly limited as long as it can be dissociated into cations and anions. The sodium salt can be, but is not limited to, sodium perchlorate, sodium hexafluorophosphate, sodium chloride, sodium fluoride, sodium sulfate, sodium carbonate, sodium phosphateSodium nitrate, sodium difluorooxalate, sodium pyrophosphate, sodium dodecylbenzenesulfonate, sodium dodecylsulfate, trisodium citrate, sodium metaborate, sodium borate, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodate, sodium iodide, sodium silicate, sodium lignosulfonate, sodium oxalate, sodium aluminate, sodium methanesulfonate, sodium acetate, sodium dichromate, sodium hexafluoroarsenate, sodium tetrafluoroborate, sodium trifluoromethanesulfonylimide, naCF 3 SO 3 Or NaN (SO) 2 CF 3 ) 2 Preferably sodium perchlorate.
Note that the electrolyte solvent is not particularly limited as long as the electrolyte solvent can dissociate the electrolyte into cations and anions, and the cations and anions can freely migrate. The preferable solvent comprises one or more of esters, sulfones, ethers or nitriles; specifically, the solvent may be, but is not limited to, propylene Carbonate (PC), ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methylethyl carbonate (EMC), methyl Formate (MF), methyl Acetate (MA), N-Dimethylacetamide (DMA), fluoroethylene carbonate (FEC), methyl Propionate (MP), ethyl Propionate (EP), ethyl Acetate (EA), γ -butyrolactone (GBL), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2 MeTHF), 1,3-Dioxolane (DOL), 4-methyl-1,3-dioxolane (4 MeDOL), dimethoxymethane (DMM), 1,2-Dimethoxypropane (DMP), triethylene glycol dimethyl ether (DG), dimethylsulfone (MSM), dimethyl ether (DME), vinyl sulfite (ES), propylene Sulfite (PS), dimethyl ether (DMS), diethyl sulfite (DES), crown ether (12-crown-4), 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-3-trifluoromethylimidazole-bis-trifluoromethanesulfonyl borate, 1-ethyl-3-methylimidazole-bis-trifluoromethanesulfonyl-3-trifluoromethanesulfonate (dmethyliminium salt, 1-methyl-3-trifluoromethanesulfonyl-bis-3-trifluoromethanesulfonate (dmethyl-propyl-3-trifluoromethanesulfonate (DME), and so as a salt, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bistrifluoromethylsulfonyl imide salt, N-butyl-N-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl-N-propylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl, propylpiperidine-bistrifluoromethylsulfonyl imide salt, or N-methyl, butylpiperidin-bistrifluoromethylsulfonyl imide salt.
Electrolyte solvent and sodium salt are preferred to enable the sodium salt to be dissolved better and enable sodium ions to migrate freely more conveniently. The concentration of sodium salt in the electrolyte is too low, the ion transmission performance is poor, and the conductivity is low; the concentration of sodium salt is too high, the ions are too much, the viscosity of the electrolyte and the degree of ion association are increased along with the increase of the concentration of sodium salt, the conductivity is reduced, and the preferable molar concentration of sodium salt can avoid the influence caused by the excessively low or high concentration of sodium salt.
In a preferred embodiment, the electrolyte further comprises an additive; the mass fraction of the additive in the electrolyte is 0.1-20%.
The mass fraction of the additive is typically, but not limited to, for example, 0.1%, 1%, 5%, 8%, 10%, 12%, 14%, 16%, 18%, or 20%.
The additive added in the electrolyte can form a stable solid electrolyte film on the surface of the negative current collector, so that the service life of the battery is prolonged. Additives include, but are not limited to, one or more of esters, sulfones, ethers, nitriles, or alkenes. Specifically, the additive may be, but is not limited to, one or more of fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, 1,3-propane sultone, 1,4-butane sultone, vinyl sulfate, propylene sulfate, ethylene sulfate, vinyl sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, dimethyl sulfoxide, anisole, acetamide, diazabenzene, m-diazabenzene, crown 12-crown-4, crown 18-crown-6, 4-fluorophenylmethyl ether, fluoro chain ether, vinyl difluoromethyl carbonate, vinyl trifluoromethylcarbonate, vinyl chlorocarbonate, vinyl bromocarbonate, trifluoroethylphosphonic acid, bromobutyrolactone, fluoroacetoxyethane, phosphate, phosphite, phosphazene, ethanolamine, dimethylamine carbide, cyclobutyl sulfone, 1,3-dioxolane, acetonitrile, long chain olefins, aluminum trioxide, magnesium oxide, barium oxide, sodium carbonate, calcium carbonate, carbon dioxide, lithium carbonate, or lithium carbonate.
Preferred separators include, but are not limited to, insulating porous polymer films or inorganic porous films, and in particular, separators include, but are not limited to, one or more of porous polypropylene films, porous polyethylene films, fiberglass paper, or porous ceramic separators. The preferable material of the diaphragm can reduce the internal resistance of the battery and prolong the cycle service life of the battery.
An exemplary method of making a sodium-ion battery includes the steps of:
(a) Preparing a sodium ion battery positive electrode: mixing a positive electrode active material, a positive electrode conductive agent, a positive electrode binder and a solvent to prepare a positive electrode material slurry, coating the positive electrode material slurry on a positive electrode current collector, and then drying, rolling and cutting to prepare a sodium ion battery positive electrode;
(b) Preparing a sodium ion battery cathode: mixing a negative electrode active material, a negative electrode conductive agent, a negative electrode binder and a solvent to prepare a negative electrode material slurry, coating the negative electrode material slurry on a negative electrode current collector, and then drying, rolling and cutting to prepare a sodium ion battery negative electrode;
(c) Preparing an electrolyte: dissolving sodium salt in a solvent, adding an additive, and mixing to obtain an electrolyte;
(d) Preparing a diaphragm: cutting and cleaning the diaphragm;
(e) And assembling the positive electrode of the sodium-ion battery, the negative electrode of the sodium-ion battery and the diaphragm, and injecting electrolyte to obtain the sodium-ion battery.
It should be noted that although steps (a) - (d) above describe the operations of the sodium ion battery preparation method in a particular order, it is not required or implied that these operations must be performed in that particular order and that the preparation of steps (a), (b), (c), (d) may be performed simultaneously or in any order.
The sodium ion battery prepared according to the preparation method of the sodium ion battery has all the effects of the sodium ion battery, and the description is omitted.
According to a sixth aspect of the present invention, there is provided an apparatus comprising a sodium ion battery.
In view of the advantages of the sodium ion battery, devices such as portable electronic devices, electrical devices, and power tools, which include the sodium ion battery, have the same advantages as the sodium ion battery.
In order to make the purpose, technical solution and beneficial technical effects of the present invention clearer, the following examples and comparative examples further illustrate the present invention in detail. It should be understood that the embodiments described in this specification are only for the purpose of explaining the present invention and are not intended to limit the present invention. The raw materials involved in the invention can be obtained commercially.
Example 1
A crystalline material of formula Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O, the preparation method comprises the following steps:
(1) 0.710g of Na 2 SO 4 、0.183g CoC 2 O 4 ·2H 2 O、0.504g H 2 C 2 O 4 ·2H 2 O and 1mL H 2 Adding O into a 50mL hydrothermal synthesis reaction kettle;
(2) Heating the reaction kettle filled with the raw materials at 200 ℃ for 72 hours, and cooling to room temperature to obtain Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O primary product;
(3) Na is mixed with 2 Co(C 2 O 4 )(SO 4 )·2H 2 Ultrasonically cleaning the O primary product by absolute ethyl alcohol, and drying to obtain pure-phase Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 And O crystal particles.
Example 2
A crystalline material of formula Na 2 Ni(C 2 O 4 )(SO 4 )·2H 2 O, raw material used in its preparation method is 0.852g Na 2 SO 4 、0.283g NiCl 2 ·6H 2 O and 0.378g H 2 C 2 O 4 ·2H 2 O, the rest is the same as example 1.
Example 3
A crystalline material of formula Na 2 Mn(C 2 O 4 )(SO 4 )·2H 2 O, the raw material used in the preparation method is Na 2 SO 4 、MnC 2 O 4 ·2H 2 O and H 2 C 2 O 4 ·2H 2 O, and the molar ratio is 6.
Example 4
A crystalline material of formula Na 2 Cu(C 2 O 4 )(SO 4 )·2H 2 O, the raw material used in the preparation method is Na 2 SO 4 、CuSO 4 And H 2 C 2 O 4 ·2H 2 O, and the molar ratio is 6.
Example 5
A crystalline material of formula Na 2 Fe 0.5 Mn 0.5 (C 2 O 4 )(SO 4 )·2H 2 O, the raw material used in the preparation method is Na 2 SO 4 、FeC 2 O 4 ·2H 2 O、MnC 2 O 4 ·2H 2 O and H 2 C 2 O 4 ·2H 2 O, and the molar ratio is 4.5.
Example 6
A crystalline material of formula Na 2 Fe 0.75 Mn 0.25 (C 2 O 4 )(SO 4 )·2H 2 O, the raw material used in the preparation method is Na 2 SO 4 、FeC 2 O 4 ·2H 2 O、MnC 2 O 4 ·2H 2 O and H 2 C 2 O 4 ·2H 2 O, and the molar ratio is 4.75.
Example 7
A crystalline material of formula Na 2 Fe 0.9 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, the raw material used in the preparation method is Na 2 SO 4 、FeC 2 O 4 ·2H 2 O、MnC 2 O 4 ·2H 2 O and H 2 C 2 O 4 ·2H 2 O, and the molar ratio is 4.9.
Example 8
A crystalline material of formula Na 2 Fe 0.9 Ti 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, the raw material used in the preparation method is Na 2 SO 4 、FeC 2 O 4 ·2H 2 O、Ti 2 (SO 4 ) 3 And H 2 C 2 O 4 ·2H 2 O, and the molar ratio is 4.
Example 9
A crystalline material of formula Na 2 Fe 0.9 V 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, the raw material used in the preparation method is Na 2 SO 4 、FeC 2 O 4 ·2H 2 O、VO 2 And H 2 C 2 O 4 ·2H 2 O, and a molar ratio of 4.9.
Example 10
A crystalline material of formula Na 2 Fe 0.9 Zn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, the raw material used in the preparation method is Na 2 SO 4 、FeC 2 O 4 ·2H 2 O、ZnSO 4 And H 2 C 2 O 4 ·2H 2 O, and a molar ratio of 4.9.
Example 11
A crystalline material of formula Na 2 Fe 0.9 Cu 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, the raw material used in the preparation method is Na 2 SO 4 、FeC 2 O 4 ·2H 2 O、CuSO 4 And H 2 C 2 O 4 ·2H 2 O, and the molar ratio is 4.9.
Example 12
A crystalline material of formula Na 2 Ti 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, the raw material used in the preparation method is Na 2 SO 4 、Ti 2 (SO 4 ) 3 、FeC 2 O 4 ·2H 2 O、MnC 2 O 4 ·2H 2 O and H 2 C 2 O 4 ·2H 2 O, and a molar ratio of 8.1.
Example 13
A crystalline material of formula Na 2 Ni 0.6 Mn 0.2 Co 0.2 (C 2 O 4 )(SO 4 )·2H 2 O, the raw material used in the preparation method is Na 2 SO 4 、NiCl 2 ·6H 2 O、MnC 2 O 4 ·2H 2 O、CoC 2 O 4 ·2H 2 O and H 2 C 2 O 4 ·2H 2 O, and a molar ratio of 4.6.
Example 14
A crystalline material of formula Na 2 V 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, the raw material used in the preparation method is Na 2 SO 4 、VO 2 、FeC 2 O 4 ·2H 2 O、MnC 2 O 4 ·2H 2 O and H 2 C 2 O 4 ·2H 2 O, and a molar ratio of 4.1.
Example 15
A crystalline material of formula Na 2 V 0.2 Fe 0.7 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, the raw material used in the preparation method is Na 2 SO 4 、VO 2 、FeC 2 O 4 ·2H 2 O、MnC 2 O 4 ·2H 2 O and H 2 C 2 O 4 ·2H 2 O, and a molar ratio of 6.2.
Example 16
A crystalline material of formula Na 2 Co(C 2 O 4 )(SO 4 )·6H 2 O, the preparation method thereof uses 5mL of water solvent, the reaction temperature is 100 ℃, and the rest is the same as the example 1.
Example 17
A crystalline material of formula Na 2 Co(C 2 O 4 )(SeO 4 )·4H 2 O, the preparation method is that sodium selenate with the same mole number is used to replace sodium sulfate, the used water solvent is 5mL, the reaction temperature is 120 ℃, and the rest is the same as the example 1.
Example 18
A crystalline material of formula Na 2 Co(C 2 O 4 )(WO 4 )·6H 2 O, the raw material used in the preparation method is Na 2 WO 4 、CoC 2 O 4 ·2H 2 O、H 2 C 2 O 4 ·2H 2 O, and the molar ratio is 6.
Example 19
A crystalline material of formula Na 2 Co(C 2 O 4 )(S 2 O 7 )·2H 2 O, the raw material used in the preparation method is Na 2 S 2 O 7 、CoC 2 O 4 ·2H 2 O、H 2 C 2 O 4 ·2H 2 O, and the molar ratio is 3.5.
Example 20
CrystalMaterial of the chemical formula Na 2 Co(C 2 O 4 )(HPO 4 )·2H 2 O, the raw material used in the preparation method is Na 2 HPO 4 、CoC 2 O 4 ·2H 2 O、H 2 C 2 O 4 ·2H 2 O, and the molar ratio is 4.5.
Example 21
A sodium ion half cell has a positive electrode active material of crystal material with chemical formula of Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O, the particle size is 500nm;
the preparation method of the sodium ion half cell comprises the following steps:
(1) Preparing a battery positive electrode: 0.8g of Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 Adding O crystal powder, 0.1g of carbon black and 0.1g of polyvinylidene fluoride into 2mL of nitrogen methyl pyrrolidone solution, and fully grinding to obtain uniform slurry; and (3) uniformly coating the slurry on the surface of an aluminum foil (a positive current collector) and then performing vacuum drying. Cutting the dried electrode slice into a wafer with the diameter of 10mm, and compacting the wafer to be used as a battery anode for standby;
(2) Preparing a diaphragm: cutting the glass fiber film into a wafer with the diameter of 16mm, and using the wafer as a diaphragm for later use;
(3) Preparing an electrolyte: 0.6122g of sodium perchlorate is weighed and added into 10mL of propylene carbonate, the sodium perchlorate is mixed and completely dissolved, 0.18g of fluoroethylene carbonate is added to be used as an additive, and the mixture is fully and uniformly mixed to be used as electrolyte for standby;
(4) Preparing a battery cathode: rolling metal sodium on an aluminum foil (negative current collector) to form a foil, and cutting the obtained sodium-aluminum composite foil into a circular sheet with the diameter of 12mm, wherein the circular sheet is used as a battery negative electrode for standby;
(5) Assembling the battery: and (3) in a glove box protected by inert gas, tightly stacking the prepared battery anode, the diaphragm and the battery cathode in sequence, dripping electrolyte to completely soak the diaphragm, and packaging the stacked part into a button cell shell to finish battery assembly.
Examples 22 to 41
A sodium ion full cell, positive electrode active material and negative electrode active material are shown in Table 1:
TABLE 1
Figure BDA0001913438660000231
Figure BDA0001913438660000241
Examples 22-41 above employed the crystalline materials provided in examples 1-20, respectively, and had a particle size of 500nm.
The method for manufacturing the sodium ion full cell provided in the above embodiments 22 to 41 includes the following steps:
(1) Preparing a battery positive electrode: adding 0.8g of crystal powder, 0.1g of carbon black and 0.1g of polyvinylidene fluoride into 2mL of nitrogen methyl pyrrolidone solution, and fully grinding to obtain uniform slurry; and (3) uniformly coating the slurry on the surface of an aluminum foil (a positive current collector) and then performing vacuum drying. Cutting the dried electrode slice into a wafer with the diameter of 10mm, and compacting the wafer to be used as a battery anode for standby;
(2) Preparing a diaphragm: cutting the glass fiber film into a wafer with the diameter of 16mm, and using the wafer as a diaphragm for later use;
(3) Preparing an electrolyte: weighing 0.6122g of sodium perchlorate into 10mL of propylene carbonate, mixing the sodium perchlorate into the mixture to be completely dissolved, adding 0.18g of fluoroethylene carbonate serving as an additive, and fully and uniformly mixing the mixture to serve as electrolyte for later use;
(4) Preparing a battery cathode: adding 0.8g of natural graphite, 0.1g of carbon black and 0.1g of polyvinylidene fluoride into 2mL of nitrogen methyl pyrrolidone solution, and fully grinding to obtain uniform slurry; uniformly coating the slurry on the surface of an aluminum foil (a negative current collector) and then carrying out vacuum drying; cutting the dried electrode slice into a wafer with the diameter of 10mm, and compacting the wafer to be used as a battery cathode for standby;
(5) Assembling the battery: and (3) in a glove box protected by inert gas, tightly stacking the prepared battery anode, the diaphragm and the battery cathode in sequence, dripping electrolyte to completely soak the diaphragm, and then packaging the stacked part into a button cell shell to finish cell assembly.
Example 42
A sodium ion full cell, differing from example 22 in that the particle size of the positive electrode crystalline material was 1000nm.
Example 43
A sodium ion full cell, which is different from example 22 in that an equimolar amount of CoCl was prepared during the preparation of a crystalline material 2 Alternative CoC 2 O 4 ·2H 2 O。
Example 44
A sodium ion full cell, differing from example 22 in that MCMB replaces natural graphite.
Comparative example 1
A sodium ion full cell, which is different from the embodiment 22 in that the anode active material is NaCoO 2 。
Comparative example 2
A sodium ion full cell, which is different from the embodiment 22 in that the positive electrode active material is Na 3 V 2 (PO 4 ) 3 。
Comparative example 3
A sodium ion full cell, which is different from the embodiment 22 in that the positive electrode active material is Na 2 C 6 H 2 O 4 。
To further verify the effects of the above examples and comparative examples, the following experimental examples were specified.
Experimental example 1 cycle performance test
The sodium ion half cell of example 21 was subjected to cycle performance test, with a charge-discharge voltage range of 2.0V to 4.5V and a charge-discharge current of 100mA/g. Fig. 5 is a graph showing the relationship between the specific charge capacity, the specific discharge capacity and the coulombic efficiency of the sodium-ion battery of example 21 at different cycle numbers.
As shown in fig. 5, the sodium-ion battery of example 21 has a first coulombic efficiency of 88%, good charge-discharge reversibility and good cycle stability.
Experimental example 2 electrochemical Performance test
The sodium ion batteries of examples 22 to 44 and comparative examples 1 to 3 were subjected to electrochemical performance tests, and the test results are shown in table 2.
The test method is as follows:
1. standard charging:
the environmental temperature is 30 +/-2 DEG C
Constant current charging
Constant current: 1C, protection conditions: cutoff voltage is not less than 4.5V
Standing for 5 minutes
2. Standard discharge:
the environmental temperature is 30 +/-2 DEG C
Constant current discharge
Constant current: 1C, protection conditions: cut-off voltage is less than or equal to 1.5V
And standing for 5 minutes.
The number of stable cycles refers to the number of cycles that can be cycled while maintaining 80% of the initial battery capacity.
TABLE 2
Figure BDA0001913438660000261
Figure BDA0001913438660000271
As can be seen from Table 2, the positive active material of the sodium-ion battery provided by the invention adopts the chemical formula of Na 2 M(C 2 O 4 )X·nH 2 And (2) a crystal material of O (wherein M is at least one positive divalent metal, X is a negative divalent anion group, n is more than or equal to 0 and less than or equal to 12) is matched with the materials of the positive electrode and the negative electrode to obtain the sodium ion full battery, which has higher working voltage, battery capacity and good cycling stability.
Examples 26 to 33 are different from example 34 in the kind and content of the metal M in the positive electrode active material, and example 34 provides a sodium-ion battery having a higher operating voltage and a higher battery capacity than those of examples 26 to 33, and also has a higher number of stable cycles of example 34, which indicates that the kind and content of the metal element M in the crystalline material as the positive electrode active material affects the electrochemical performance of the sodium-ion battery.
Examples 35 and 36 differ from example 22 in that the positive electrode active material differs, and the resulting sodium ion battery differs in electrochemical performance, operating voltage, battery capacity and number of stable cycles. The sodium ion battery provided by the embodiment 22 has the highest stability of the cycling performance, and the working voltage and the battery capacity of the sodium ion battery provided by the embodiment 22 and the embodiments 35 and 36 are not greatly different.
Example 37 is different from example 22 in the content of crystal water of the positive electrode active material; examples 38 and 39 are different from example 22 in the content of the cathode ion group and the crystal water content of the positive electrode active material; examples 40 and 41 are different from example 22 in that the cathode ion group of the cathode active material is different; the electrochemical performance of the sodium-ion battery of example 22 was better than that of the sodium-ion batteries of examples 37 to 41, indicating that the crystal water content of the positive electrode active material and the kind of the anionic group affect the electrochemical performance of the sodium-ion battery.
Example 42 is different from example 22 in the particle size of the positive electrode active material; example 43 differs from example 22 in the cobalt source used to prepare the positive electrode active material; example 44 is different from example 22 in that the anode active material is different. The working voltage, battery capacity and number of stable cycles were slightly higher for example 22 than for example 42; the operating voltage, cell capacity and number of stable cycles of example 22 were not significantly different from examples 43, indicating that the particle size of the positive active material, the metal M-containing starting material and the negative active material had an effect on the electrochemical performance of the sodium ion battery, but were not significant.
Comparative example 1 is different from example 22 in that the positive electrode active material is a layered oxide containing sodium and cobalt; comparative example 2 is different from example 22 in that the positive electrode active material is an existing polyanion compound; the comparative example 3 is different from the example 22 in that the cathode active material is an existing organic cathode material. The sodium ion batteries of comparative examples 1-3 all had significantly less high numbers of stable cycles than example 22, and the operating voltages and battery capacities of the sodium ion batteries of comparative examples 1,2 were not significantly different from example 22, and the operating voltage and battery capacity of the sodium ion battery of comparative example 3 were significantly lower than that of the sodium ion battery of example 22. This shows that the structural stability of the cathode active material prepared from the crystalline material provided by the present invention is higher than that of the cathode active material of the comparative example.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (11)

1. A crystalline material, characterized in that the crystalline material has the chemical formula Na 2 M(C 2 O 4 )X·nH 2 O, wherein M is a combination of Fe, ti, V, cr, mn, co, ni, cu and Zn, and X is (SO) 4 )、(SeO 4 )、(PO 3 F)、(HPO 4 )、(HAsO 4 )、(MoO 4 )、(WO 4 )、(S 2 O 7 )、(Se 2 O 7 ) N is more than or equal to 0 and less than or equal to 12, the crystal material belongs to heterogeneous isomorphism, macroscopically presents a hexagonal prism shape or a square prism shape, belongs to a hexagonal crystal system, and has a three-dimensional framework structure, and the crystal material is prepared by adopting the following steps:
uniformly mixing a sodium source, an M source, an oxalate source, an X source and a solvent, and then carrying out a solvothermal reaction to obtain the crystal material;
the molar ratio of the sodium source, the M source, the oxalate source and the X source is (2-8) to 1 (1-8) to (2-8);
the sodium source comprises at least one of a sodium-containing oxide, base, or salt;
the M source comprises at least one of an oxide, an acid, a base, a salt or a simple substance M containing M;
the oxalate source comprises at least one of an oxalate-containing acid or salt;
the source of X comprises at least one of an X-containing acid or salt;
the solvent is at least one of water, alcohols, ketones or pyridines.
2. A crystalline material as claimed in claim 1, characterised in that 0. Ltoreq. N.ltoreq.6.
3. Crystalline material according to claim 2, characterized in that it has the formula Na 2 Fe 0.5 Mn 0.5 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Fe 0.75 Mn 0.25 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Fe 0.9 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Fe 0.9 Ti 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Fe 0.9 V 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Fe 0.9 Zn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Fe 0.9 Cu 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Ti 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 Ni 0.6 Mn 0.2 Co 0.2 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 V 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O、Na 2 V 0.2 Fe 0.7 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 And O is one of the compounds.
4. A crystalline material as claimed in claim 1 wherein said solvent is water.
5. A crystalline material as claimed in claim 1, wherein said solvothermal temperature is in the range 100 to 300 ℃ for a period of 4 to 100 hours.
6. A crystalline material as claimed in claim 5, wherein said solvothermal temperature is in the range 180 to 220 ℃ for a period of 48 to 72 hours.
7. Use of the crystalline material of any one of claims 1-6 in the preparation of a positive electrode active material.
8. A positive electrode material for a sodium-ion battery, comprising the crystalline material according to any one of claims 1 to 6.
9. The positive electrode material for sodium-ion batteries according to claim 8, comprising a positive electrode active material, a positive electrode conductive agent and a positive electrode binder; the weight ratio of the positive active material, the positive conductive agent and the positive binder is (60-90): 5-30): 3-10; the positive active material is the crystalline material;
the positive electrode conductive agent comprises at least one of conductive carbon black, conductive carbon spheres, conductive graphite, conductive carbon fibers, carbon nanotubes, graphene and reduced graphene oxide;
the positive binder comprises at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose and styrene butadiene rubber.
10. A sodium-ion battery comprising the positive electrode material for a sodium-ion battery according to claim 8 or 9.
11. An apparatus comprising the sodium ion battery of claim 10.
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