CN114906880A - Preparation method of positive electrode material of sodium-ion battery and sodium-ion battery - Google Patents
Preparation method of positive electrode material of sodium-ion battery and sodium-ion battery Download PDFInfo
- Publication number
- CN114906880A CN114906880A CN202210366724.2A CN202210366724A CN114906880A CN 114906880 A CN114906880 A CN 114906880A CN 202210366724 A CN202210366724 A CN 202210366724A CN 114906880 A CN114906880 A CN 114906880A
- Authority
- CN
- China
- Prior art keywords
- sodium
- temperature
- mixed solution
- ion battery
- gel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a preparation method of a sodium ion battery anode material and a sodium ion battery, wherein the preparation method comprises the following steps: dissolving a sodium source, a nickel source and a manganese source in deionized water to form a mixed solution; vigorously stirring the mixed solution, adding a complexing agent into the mixed solution during vigorous stirring, and keeping the pH value of the mixed solution at 8-9; evaporating and concentrating the mixed solution added with the complexing agent to prepare gel, and drying the gel; and pre-burning the dried gel at a first temperature and preserving heat for a first time period, and then calcining at a second temperature and preserving heat for a second time period to obtain the final cathode material. The preparation method and the sodium ion battery provided by the invention have the advantages that the prepared anode material is good in appearance, and the charging and discharging performance of the battery is excellent.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of batteries, in particular to a preparation method of a sodium-ion battery anode material and a sodium-ion battery.
[ background of the invention ]
The lithium battery has the advantages of long cycle life, energy conservation, environmental protection, no pollution, low maintenance cost, complete charging and discharging, light weight and the like, and compared with the lithium element in the lithium battery, the sodium element has richer resources, low cost and wide distribution, and the sodium element and the lithium element belong to the same main group of the periodic table of elements, have similar physical and chemical properties and are expected to replace the lithium battery.
The positive electrode material of the sodium ion battery mainly comprises NaMO 2 (M is Co, Ni, Fe, Mn, etc.), metal fluoride, polyanion type material, etc., wherein, NaMO 2 The transition metal is doped, the doping amount of the transition metal and the synthesis method of the cathode material all have important influence on the electrochemical performance of the cathode material.
In view of the above, it is necessary to provide a novel method for preparing a positive electrode material of a sodium ion battery and a sodium ion battery to overcome the above-mentioned drawbacks.
[ summary of the invention ]
The invention aims to provide a preparation method of a sodium ion battery anode material and a sodium ion battery.
In order to achieve the above object, in a first aspect, the present invention provides a method for preparing a positive electrode material of a sodium ion battery, including the steps of: dissolving a sodium source, a nickel source and a manganese source in deionized water to form a mixed solution; vigorously stirring the mixed solution, adding a complexing agent into the mixed solution during vigorous stirring, and keeping the pH value of the mixed solution at 8-9; evaporating and concentrating the mixed solution added with the complexing agent to prepare gel, and drying the gel; pre-burning the dried gel at a first temperature and preserving heat for a first time period, then calcining at a second temperature and preserving heat for a second time period to prepare a final anode material; in the final cathode material, the molar ratio of the sodium element to the nickel element to the manganese element is 0.46:0.26: 0.54.
In a preferred embodiment, the complexing agent is citric acid monohydrate.
In a preferred embodiment, the mixed solution is vigorously stirred, and in the step of adding the complexing agent to the mixed solution during the vigorous stirring and maintaining the pH of the mixed solution at 8 to 9, the pH of the mixed solution is maintained at 8 to 9 by adding ammonia water.
In a preferred embodiment, the mixed solution after the complexing agent is added is subjected to evaporation concentration to prepare gel, and the step of drying the gel is carried out, wherein the temperature of the evaporation concentration is 80-100 ℃, and the temperature of the drying is 110-130 ℃.
In a preferred embodiment, in the step of preparing the final cathode material, the dried gel is pre-sintered at a first temperature and is subjected to heat preservation for a first period of time, and then is calcined at a second temperature and is subjected to heat preservation for a second period of time, wherein the first temperature is 400 ℃, and the first period of time is 5 hours.
In a preferred embodiment, in the step of preparing the final cathode material, the dried gel is pre-sintered at a first temperature and is kept at a first time period, and then is calcined at a second temperature and is kept at a second time period, wherein the second temperature is 900 ℃, and the second time period is 14 hours.
In a second aspect, the invention also provides a sodium-ion battery, which comprises a positive plate, wherein the positive plate is coated with the positive material prepared by the preparation method of the sodium-ion battery positive material.
In a preferred embodiment, the sodium-ion battery further comprises a negative electrode sheet and a diaphragm, wherein the positive electrode sheet, the diaphragm and the negative electrode sheet are wound in sequence to manufacture the sodium-ion battery.
Compared with the prior art, the preparation method of the sodium ion battery anode material and the sodium ion battery provided by the invention have the advantages that the sodium source, the nickel source and the manganese source are firstly dissolved in deionized water to form a mixed solution, nickel and manganese are selected for doping, the manganese element is abundant in storage capacity in the earth crust, non-toxic and high in specific capacity, active nickel in the transition metal layer can be used for inhibiting the manganese from being dissolved under high voltage, the structure of the final anode material can be further stabilized, the electrochemical performance of the anode material is improved, the mixed solution is stirred vigorously, a complexing agent is added into the mixed solution in the vigorous stirring process, the pH value of the mixed solution is kept between 8 and 9, the gel is prepared by evaporation and concentration and then is dried, the three raw materials are mixed in a liquid phase, the distribution of all elements can be more uniform, the ion mixing probability is promoted, and the influence of local lattice distortion on the material structure is reduced, and finally, pre-burning the dried gel at a first temperature and preserving heat for a first time period, and then calcining at a second temperature and preserving heat for a second time period to prepare a final anode material, wherein impurities in the material can be removed through pre-burning, so that the material subjected to secondary calcination has a more stable structure, has a wider crystal structure after being sintered into a phase, and improves the electrochemical performance of the anode material.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
[ description of the drawings ]
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a flow chart of a method for preparing the positive electrode material of the sodium-ion battery provided by the invention;
FIG. 2 is an XRD pattern of a cathode material prepared by an example and a comparative example provided by the invention;
FIG. 3 is an SEM image of a positive electrode material prepared by an example and a comparative example provided by the invention;
fig. 4a and 4b are CV graphs of batteries prepared by using the positive electrode materials of the examples and comparative examples provided by the invention;
FIG. 5 is a graph showing the first charge and discharge performance of batteries fabricated using the positive electrode materials of examples and comparative examples provided in the present invention;
fig. 6 is a graph showing the cycle performance of batteries prepared from the positive electrode materials of examples and comparative examples provided by the invention.
[ detailed description ] A
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. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the present invention provides a method for preparing a positive electrode material of a sodium ion battery, which is used for preparing a positive electrode active material of the sodium ion battery. Specifically, the preparation method of the positive electrode material of the sodium-ion battery comprises the following steps:
step S10: dissolving a sodium source, a nickel source and a manganese source in deionized water to form a mixed solution. Specifically, the sodium source may be Na 2 CO 3 The nickel source may be Ni (CH) 3 COO) 2 ·4H 2 O, the manganese source can be Mn (CH) 3 COO) 2 ·4H 2 O, namely weighing Na according to a certain stoichiometric ratio 2 CO 3 、Ni(CH 3 COO) 2 ·4H 2 O and Mn (CH) 3 COO) 2 ·4H 2 Dissolving O in deionized water to form a mixed solution.
Step S20: and (2) vigorously stirring the mixed solution, adding a complexing agent into the mixed solution during vigorous stirring, and keeping the pH value of the mixed solution at 8-9. Specifically, the mixed solution prepared in step S10 is accelerated and vigorously stirred, and a complexing agent is added during the stirring process, wherein the complexing agent can form complex ions with metal ions, and the pH of the mixed solution is ensured to be 8-9.
Step S30: and evaporating and concentrating the mixed solution added with the complexing agent to prepare gel, and drying the gel. Specifically, the mixed solution added with the complexing agent can form gel after evaporation concentration, and the prepared gel is placed into an oven for drying, wherein the temperature of evaporation concentration is 80-100 ℃, and the temperature of drying is 110-.
Step S40: and pre-burning the dried gel at a first temperature and preserving heat for a first time period, and then calcining at a second temperature and preserving heat for a second time period to obtain the final cathode material. Specifically, the dried gel is pre-sintered at a lower temperature, then is calcined at a higher temperature, and is ground and sieved after being cooled to room temperature, so that the final cathode material is prepared.
The invention provides a preparation method of a sodium ion battery anode material, which comprises the steps of firstly dissolving a sodium source, a nickel source and a manganese source in deionized water to form a mixed solution, selecting nickel and manganese for doping, wherein the manganese element is rich in reserve in earth crust, non-toxic and high in specific capacity, active nickel in a transition metal layer can inhibit the manganese from dissolving under high voltage, further the structure of the final anode material can be stabilized, the electrochemical performance of the anode material is improved, then the mixed solution is vigorously stirred, a complexing agent is added into the mixed solution in the vigorous stirring process, the pH value of the mixed solution is kept between 8 and 9, the gel is prepared by evaporation and concentration and then dried, and the three raw materials are mixed in a liquid phase to ensure that the elements are distributed more uniformly, the probability of ion mixing and discharging is promoted, and the influence of local lattice distortion on the material structure is reduced, and finally, pre-burning the dried gel at a first temperature and preserving heat for a first time period, and then calcining at a second temperature and preserving heat for a second time period to prepare a final anode material, wherein impurities in the material can be removed through pre-burning, so that the material subjected to secondary calcination has a more stable structure, has a wider crystal structure after being sintered into a phase, and improves the electrochemical performance of the anode material.
Further, in the step of vigorously stirring the mixed solution and adding a complexing agent to the mixed solution during vigorous stirring and maintaining the pH of the mixed solution at 8 to 9 (i.e., step S20), the pH of the mixed solution is maintained at 8 to 9 by adding ammonia water, and the complexing agent is citric acid monohydrate. It is understood that the complexing agent can form complex ions with metal ions, so that the mixed solution forms gel, and the pH value of the mixed solution can be adjusted by adding ammonia water, so as to provide an alkaline environment.
Further, in the step of evaporating and concentrating the mixed solution added with the complexing agent to obtain a gel and drying the gel (i.e., step S30), the gel may be obtained by evaporating and concentrating at 85 ℃ and then drying the gel in an oven at 120 ℃ for about 24 hours to completely dry the gel.
Further, in the step (i.e., step S40) of pre-burning the dried gel at a first temperature and keeping the temperature for a first time period, then calcining at a second temperature and keeping the temperature for a second time period to obtain the final cathode material, the first temperature is 400 ℃, the first time period is 5 hours, the second temperature is 900 ℃, the second time period is 14 hours, i.e., the gel is pre-burned at 400 ℃, kept the temperature for 5 hours, then heated to 900 ℃, kept the temperature for 14 hours, and H in the sample can be removed by pre-burning 2 O、NH 4 And CO 2 And moreover, by setting a higher calcining temperature and a longer heat preservation time, the phenomenon of agglomeration of the material at a lower temperature can be avoided, and the anode material with regular appearance and uniform size can be obtained.
Furthermore, in the cathode material prepared by the preparation method of the cathode material for the sodium-ion battery, the molar ratio of the sodium element, the nickel element and the manganese element is 0.46:0.26:0.54, namely the chemical formula of the cathode material is Na 0.46 Ni 0.26 Mn 0.54 O 2 It can be understood that the doping amount of nickel and manganese can be reasonably controlled, that is, the sodium content in the material can be adjusted, and the appropriate sodium content can optimize the structure of the material and improve the electrochemical performance of the cathode material.
The invention also provides a sodium ion battery which comprises a positive plate, wherein the positive plate is coated with the positive material prepared by the preparation method of the sodium ion battery positive material. The sodium-ion battery also comprises a negative plate and a diaphragm, wherein the positive plate, the diaphragm and the negative plate are sequentially wound to form the sodium-ion battery.
Specifically, the positive electrode material prepared by the preparation method is mixed with a conductive additive and a binder according to a ratio of 90:5:5, the mixture is added into a solvent for dissolution, a positive electrode plate is prepared by the process flows of pulping, smearing, drying and the like, and then a sodium foil is used as a negative electrode, glass fiber is used as a diaphragm, and the sodium ion battery is assembled after electrolyte is injected. It is understood that the conductive additive may be one or more of carbon black, Super-P, ketjen black, the binder may be one or more of polyvinylidene fluoride (PVDF) or polyacrylic acid (PAA), sodium carboxymethylcellulose (CMC), Sodium Alginate (SA), preferably PVDF, the solvent is N-methylpyrrolidone, and the matrix of the positive electrode sheet is aluminum foil.
The invention will now be described and verified with reference to specific examples.
Example (b): weighing Na 2 CO 3 、Ni(CH 3 COO) 2 ·4H 2 O and Mn (CH) 3 COO) 2 ·4H 2 Dissolving O in deionized water, stirring for about 15min, dropping a certain amount of citric acid monohydrate aqueous solution in the prepared solution with acceleration and vigorous stirring for about 2h, adding ammonia water in the dropping process, controlling the pH to be stable at 8-9, evaporating the solution in a beaker to dryness after the solution is formed into a sol water bath, putting the beaker and a sample in a vacuum drying box at 80 ℃, drying for about 24h, grinding and sieving the sample after the solution is completely dried, putting the sample in a small porcelain boat for presintering at 400 ℃, preserving the heat for 5h, then heating to 900 ℃, preserving the heat for 14h, grinding the sample after the sample is cooled to room temperature and sieving the sample with a 300-mesh (0.055mm) sieve to obtain the final anode material Na 0.46 Ni 0.26 Mn 0.54 O 2 。
The positive electrode material Na prepared in example was weighed according to a ratio of 90:5:5, respectively 0.46 Ni 0.26 Mn 0.54 O 2 Putting the SP and the PVDF in a beaker, adding NMP as a solvent for dissolving, performing planetary milling for 10 hours, and fully mixing the slurryCoating on aluminum foil after mixing uniformly, cutting into positive plate by a cutting machine after drying, and then taking sodium foil as negative electrode and electrolyte as NaClO 6 The batteries were assembled in a glove box using VMP32340 glass fiber as a separator to prepare example batteries.
Comparative example: substantially the same as the preparation method of the example except that the raw material further includes Fe 2 (C 2 O 4 ) 3 ·5H 2 O, and the final anode material is Na 0.46 Ni 0.13 Fe 0.13 Mn 0.54 O 2 And a comparative example battery was prepared. It is understood that in the comparative example, three elements of nickel, iron and manganese are used for doping, but the sodium content is the same as that of the example.
Referring to fig. 2, which is an XRD pattern of the cathode material prepared in the examples and comparative examples provided in the present invention, it can be seen from fig. 2 that the cathode material Na prepared in the examples 0.46 Ni 0.26 Mn 0.54 O 2 Respectively, are 157 °, 31.7 °, 35.9 °, 39.4 °, 43.4 °, 48.6 °, respectively, corresponding to [002 °]、[004]、[100]、[102]、[103]、[104]The structure of the anode material prepared in the embodiment completely corresponds to the structure of a layered P2 type, and the diffraction peak is very sharp, which indicates that the material prepared by the sol-gel method in the embodiment of the invention has the P2 type layered material, the crystallinity is better, meanwhile, the heat preservation time is increased during the secondary calcination heat preservation, the crystal of the material can grow better, the sodium ions occupy the prism positions, and the sodium ions can diffuse from the centers of the triangular prisms during the discharge, so that the distance between the two atomic layers is changed. And the positive electrode material Na prepared in the comparative example 0.46 Ni 0.13 Fe 0.13 Mn 0.54 O 2 There is a shift in diffraction peaks of (a) and many peaks of (b) occur, and there is a possibility that the diffraction peaks are generated due to a change in the interplanar spacing of the material and that the electrostatic repulsive force of the negative charge is changed by iron ions, and the material does not belong to the P2 type structure.
Please refer to fig. 3, which is an SEM image of the cathode materials prepared in the examples and comparative examples provided in the present invention, wherein fig. 3a is the cathode material prepared in the examplesMaterial Na 0.46 Ni 0.26 Mn 0.54 O 2 In the microscopic view, it can be seen that the positive electrode material Na 0.46 Ni 0.26 Mn 0.54 O 2 The micro-morphology is complete, the particles are uniform and clear, the electrolyte can completely enter the material in the process of manufacturing the battery, the performance of the battery is optimized, and fig. 3b shows the positive electrode material Na prepared by the comparative example 0.46 Ni 0.13 Fe 0.13 Mn 0.54 O 2 The microscopic picture shows that the material added with the ferric oxalate is more obvious in agglomeration, the sheet shape of the material is thicker, and micropores and mesopores are also formed by agglomeration. The material morphology of the examples is superior to the comparative examples.
Please refer to fig. 4a and 4b, which are CV graphs of batteries prepared by the positive electrode materials of examples and comparative examples provided by the present invention. Wherein, FIG. 4a shows the positive electrode material Na prepared in the example 0.46 Ni 0.26 Mn 0.54 O 2 As can be seen from the CV curve graphs, the 1 st curve and the 2 nd curve are better overlapped, the main reason is that the material has a P2 type structure, so that the material has better cycle performance and better structural stability, and when the voltage is 2.25-2.5V, Mn is in positive sweep of the CV curve 3+ By oxidation to Mn 4+ Mn is also added during negative sweeping 4+ Reduction to Mn 3+ . FIG. 4b shows a positive electrode material Na prepared in a comparative example 0.46 Ni 0.13 Fe 0.13 Mn 0.54 O 2 In the CV curve graphs, it can be seen that the cycle curves of the 1 st and the 2 nd times are not overlapped, which indicates that irreversible capacity exists for the first time, the peak area exists in an SEI film, and the peak area in the interval of 3.0-4.0V is reduced compared with the CV area of the example, which indicates that the material added with the iron element does not improve the stability of the material, but rather, the electrochemical performance of the material is affected.
Please refer to fig. 5, which is a graph illustrating the first charge and discharge performance of the battery prepared by the positive electrode material of the example and the comparative example provided by the present invention. It can be seen that the first charge voltage of the example cell was 163mAh/g, and the first charge voltage of the comparative example cell was 125 mAh/g. Therefore, in the preparation process of the precursor, the Fe ions are added, so that the structure of the material is changed and is not a P2-type layered structure any more, the surface morphology of the particles is changed, and the electrochemical performance of the battery prepared from the material is greatly influenced by the change of the structure and the morphology.
Please refer to fig. 6, which is a graph illustrating the cycle performance of the battery prepared by the positive electrode material of the example and the comparative example provided by the present invention. It can be seen that the first reversible specific capacity of the battery in the embodiment reaches about 200mAh/g, the charge-discharge efficiency is 92%, the discharge specific capacity of the material begins to decrease after slightly increasing with the increase of the cycle times, about 180mAh/g still exists after 50 cycles, the charge-discharge efficiency is 85%, and the battery has better cycle performance. The first reversible capacity of the comparative example battery is lower and is only about 100mAh/g, the charge-discharge efficiency is 93%, and after 50 times of circulation, the charge-discharge efficiency is about 87mAh/g and is 92.45%.
In summary, the sodium ion battery and the preparation method of the positive electrode material thereof provided by the invention ensure reasonable sodium content by doping nickel and manganese in a proper amount, and synthesize the material Na by adopting a sol-gel method 0.46 Ni 0.26 Mn 0.54 O 2 The secondary calcination temperature is 900 ℃, the heat preservation time is 14 hours, the obtained material has a hexagonal layered P2 type structure, the particle surface is smooth, the infiltration of electrolyte is facilitated, the proper calcination temperature and time can ensure the sufficient growth contact and reaction of the material and reduce the generation of impurity phases, so the electrochemical performance of the material is improved, the first reversible specific capacity of the prepared battery reaches 200mAh/g, after 50 times of circulation, the circulation efficiency is 85%, the discharge curve is smooth, the impedance is small, and the discharge specific capacity is very high.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (8)
1. A preparation method of a positive electrode material of a sodium-ion battery is characterized by comprising the following steps:
dissolving a sodium source, a nickel source and a manganese source in deionized water to form a mixed solution;
vigorously stirring the mixed solution, adding a complexing agent into the mixed solution during vigorous stirring, and keeping the pH value of the mixed solution at 8-9;
evaporating and concentrating the mixed solution added with the complexing agent to prepare gel, and drying the gel;
pre-burning the dried gel at a first temperature and preserving heat for a first time period, then calcining at a second temperature and preserving heat for a second time period to prepare a final anode material; in the final cathode material, the molar ratio of the sodium element, the nickel element and the manganese element is 0.46:0.26: 0.54.
2. The method of claim 1, wherein the complexing agent is citric acid monohydrate.
3. The method according to claim 1, wherein the mixed solution is vigorously stirred, and the complexing agent is added to the mixed solution during the vigorous stirring, and the pH of the mixed solution is maintained at 8 to 9 by adding ammonia water in the step of maintaining the pH of the mixed solution at 8 to 9.
4. The method for preparing the positive electrode material of the sodium-ion battery as claimed in claim 1, wherein the mixed solution added with the complexing agent is evaporated and concentrated to prepare the gel, and the step of drying the gel is carried out at the temperature of 80-100 ℃ for evaporation and concentration and at the temperature of 110-130 ℃.
5. The method for preparing the positive electrode material of the sodium-ion battery according to claim 1, wherein in the step of preparing the final positive electrode material, the dried gel is pre-sintered at a first temperature and is kept at the first temperature for a first period of time, and then is calcined at a second temperature and is kept at the second temperature for a second period of time, wherein the first temperature is 400 ℃ and the first period of time is 5 hours.
6. The method for preparing the positive electrode material of the sodium-ion battery according to claim 5, wherein in the step of preparing the final positive electrode material, the dried gel is pre-sintered at a first temperature and is kept at the first temperature for a first period of time, and then is calcined at a second temperature and is kept at the second temperature for a second period of time, wherein the second temperature is 900 ℃, and the second period of time is 14 hours.
7. A sodium-ion battery, which is characterized by comprising a positive plate, wherein the positive plate is coated with the positive material prepared by the preparation method of the positive material for the sodium-ion battery according to any one of claims 1 to 7.
8. The sodium-ion battery of claim 7, further comprising a negative plate and a separator, wherein the positive plate, the separator and the negative plate are wound in sequence to form the sodium-ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210366724.2A CN114906880A (en) | 2022-04-08 | 2022-04-08 | Preparation method of positive electrode material of sodium-ion battery and sodium-ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210366724.2A CN114906880A (en) | 2022-04-08 | 2022-04-08 | Preparation method of positive electrode material of sodium-ion battery and sodium-ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114906880A true CN114906880A (en) | 2022-08-16 |
Family
ID=82763364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210366724.2A Withdrawn CN114906880A (en) | 2022-04-08 | 2022-04-08 | Preparation method of positive electrode material of sodium-ion battery and sodium-ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114906880A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117228745A (en) * | 2023-11-10 | 2023-12-15 | 蜂巢能源科技股份有限公司 | Sodium ion battery anode sodium supplementing agent and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711440A (en) * | 2017-01-20 | 2017-05-24 | 东莞市迈科新能源有限公司 | Nano flaky sodium-ion battery anode material and preparation method thereof |
| CN111180704A (en) * | 2020-01-07 | 2020-05-19 | 湖南工程学院 | Sodium-ion battery positive electrode material and preparation method and application thereof |
-
2022
- 2022-04-08 CN CN202210366724.2A patent/CN114906880A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711440A (en) * | 2017-01-20 | 2017-05-24 | 东莞市迈科新能源有限公司 | Nano flaky sodium-ion battery anode material and preparation method thereof |
| CN111180704A (en) * | 2020-01-07 | 2020-05-19 | 湖南工程学院 | Sodium-ion battery positive electrode material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| P.MANIKANDAN ET AL.: "Layered P2-type Na0.5Ni0.25Mn0.75O2 as a high performance cathode material for sodium-ion batteries", 《ELECTROCHIMICA ACTA》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117228745A (en) * | 2023-11-10 | 2023-12-15 | 蜂巢能源科技股份有限公司 | Sodium ion battery anode sodium supplementing agent and preparation method and application thereof |
| CN117228745B (en) * | 2023-11-10 | 2024-01-23 | 蜂巢能源科技股份有限公司 | Sodium ion battery anode sodium supplementing agent and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11380881B2 (en) | Anode material of lithium ion battery and non-aqueous electrolyte battery | |
| CN111435740B (en) | Positive electrode active material, positive plate and sodium ion battery | |
| CN110416503B (en) | Soft carbon coated sodium titanium phosphate mesoporous composite material and preparation method and application thereof | |
| BRPI0919655B1 (en) | Olivine-type lithium iron phosphate, cathode mixture, secondary lithium battery and method for preparing lithium iron phosphate | |
| CN112768687A (en) | Lithium-site-doped modified high-nickel low-cobalt ternary cathode material for lithium ion battery and preparation method thereof | |
| CN101863518A (en) | Co3O4 nano hollow sphere material and preparation method and application thereof | |
| CN115224254B (en) | Cu, zn and Mg co-doped layered oxide sodium ion battery positive electrode material, and preparation method and application thereof | |
| WO2016176928A1 (en) | Negative electrode material, preparation method therefor, and lithium-ion secondary battery using the negative electrode material | |
| WO2016188130A1 (en) | Preparation method for porous graphite-doped and carbon-coated lithium titanate negative electrode material | |
| TW202141831A (en) | Lithium battery and anode material thereof | |
| CN113443662B (en) | Preparation method of sodium and/or potassium doped high-nickel ternary positive electrode material | |
| CN103693632B (en) | A kind of preparation method of lithium vanadyl phosphate positive material for lithium ion battery | |
| CN113066980B (en) | Method for preparing phosphomolybdic acid modified high-nickel single crystal positive electrode material | |
| CN114906880A (en) | Preparation method of positive electrode material of sodium-ion battery and sodium-ion battery | |
| CN114275829B (en) | Hollow spherical high-entropy oxide with microporated surface, and preparation method and application thereof | |
| CN108172813B (en) | Composite cathode material and preparation method thereof | |
| CN116154154A (en) | Pure-phase polyanion type sulfate sodium ion battery positive electrode material and preparation method thereof | |
| CN114678524A (en) | High-nickel positive electrode material and preparation method thereof | |
| CN114864911A (en) | Modified high-nickel ternary cathode material and preparation method and application thereof | |
| CN109461897B (en) | Preparation method of spindle-shaped carbon-coated vanadium-based positive electrode material | |
| CN114014330A (en) | Energy storage electrode material K3Nb3Si2O13Preparation method and application of | |
| CN108011096B (en) | Porous cubic lithium battery cathode material lithium nickel manganese oxide and preparation method thereof | |
| CN113488642A (en) | Lithium ion quaternary positive electrode material, preparation method thereof and lithium ion battery | |
| CN118239524B (en) | Lithium-rich manganese-based positive electrode material and preparation method and application thereof | |
| CN118073552B (en) | Sodium ion battery positive electrode material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 523000 buildings C and D, No.18 zhongkeng Road, Sanzhong village, Qingxi Town, Dongguan City, Guangdong Province Applicant after: Dongguan Langtaitong Technology Co.,Ltd. Address before: 523000 buildings C and D, No.18 zhongkeng Road, Sanzhong village, Qingxi Town, Dongguan City, Guangdong Province Applicant before: DONGGUAN WOTAITONG NEW ENERGY Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20220816 |
|
| WW01 | Invention patent application withdrawn after publication |