CN116130644A - Sodium ion battery positive electrode material and preparation method thereof - Google Patents

Sodium ion battery positive electrode material and preparation method thereof Download PDF

Info

Publication number
CN116130644A
CN116130644A CN202211550255.6A CN202211550255A CN116130644A CN 116130644 A CN116130644 A CN 116130644A CN 202211550255 A CN202211550255 A CN 202211550255A CN 116130644 A CN116130644 A CN 116130644A
Authority
CN
China
Prior art keywords
sodium ion
positive electrode
ion battery
electrode material
sodium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211550255.6A
Other languages
Chinese (zh)
Inventor
沈晞
蒋露霞
张小兵
王晶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nantong Maolue Technology Co ltd
Original Assignee
Nantong Maolue Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nantong Maolue Technology Co ltd filed Critical Nantong Maolue Technology Co ltd
Priority to CN202211550255.6A priority Critical patent/CN116130644A/en
Publication of CN116130644A publication Critical patent/CN116130644A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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

In order to solve the problem of poor cycle performance of the existing sodium ion battery anode material, the invention provides a sodium ion battery anode material, wherein the general formula of the anode material is as follows: (Na) x Ca y K z )Me 1‑γ O 2‑σ In the general formula, x+y+z is more than or equal to 0.5 and less than or equal to 1, the material is of a layered oxide crystal structure, and Na is x Ca y K z The Me is a metal element and occupies the same layer as Na x Ca y K z Adjacent layers of the layer; the sodium ion battery anode material provided by the invention passes throughDoping a precursor of a potassium source and/or a precursor of a calcium source, wherein the doped element is used as a support column of a sodium ion layer, so that the whole phase change process of the material is prevented in the circulating process, and the stability of a crystal lattice is protected; because the ionic radius of the calcium ion and the potassium ion is similar to that of the sodium ion, the difference between the calcium ion and the potassium ion and the transition metal is large, the calcium ion and the potassium ion can only enter the sodium ion layer but not enter the transition metal layer in the synthesis process, so that the stability of the positive electrode material of the sodium ion battery is greatly improved, and the cycle life of the sodium ion battery is prolonged.

Description

Sodium ion battery positive electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a sodium ion battery anode material.
Background
Sodium ion batteries are expected to be a new generation of battery technology due to their lower cost, greater abundance and worldwide uniform distribution compared to lithium ion batteries. In the aspect of the current sodium ion battery anode material, the cycle life of the most promising layered oxide anode material is still lower, and the lithium ion battery can not be replaced in many scenes, especially in the energy storage scene.
In the current scheme, the optimization and modification of the layered oxide positive electrode of the sodium ion battery mainly focuses on the regulation of the type and proportion of cations in the transition metal layer. However, in the positive electrode of the sodium ion battery, the layer spacing is changed most greatly by a sodium ion layer in the cyclic process, so that the material is subjected to irreversible phase change, thereby damaging the crystal lattice and reducing the service life of the battery. The control of the transition metal layer cannot fundamentally solve the recycling problem of the material. Therefore, how to overcome the above-mentioned technical problems and drawbacks becomes an important problem to be solved.
Disclosure of Invention
Aiming at the problem of poor cycle performance of the sodium ion battery anode material, the invention provides the sodium ion battery anode material.
The technical scheme adopted by the invention for solving the technical problems is as follows: a positive electrode material for a sodium ion battery, the positive electrode material having the formula: (Na) x Ca y K z )Me 1-γ O 2-σ In the general formula, x+y+z is more than or equal to 0.5 and less than or equal to 1, and the value range of x is [0.5,1 ]]The value range of y is [0,0.1 ]]The value range of z is [0,0.3]And y and z are not both 0, said gammaThe value range of the sigma and sigma is [ -0.3,0.3]And Me is a metal element.
Optionally, the elements within the brackets occupy a sodium ion layer.
Optionally, the Me is selected from at least one of Fe, cu, mn, ni, co, li, mg, ti, sc, V, cr, zn, Y, zr, nb, mo.
Optionally, the positive electrode material crystal is composed of a transition metal layer and a sodium ion layer, wherein the transition metal ions occupy the transition metal layer, the sodium ions occupy the sodium ion layer, the oxygen atoms are located around the transition metal ions, and the oxygen atoms and the metal ions are connected through a metal-oxygen (Me-O) bond.
The preparation method of the sodium ion battery anode material comprises the following operations:
preparing a sodium ion battery anode material by adopting a sodium source and a Me source through a solid phase method or a coprecipitation and solid phase method and sintering;
wherein at least one of a potassium source and a calcium source is doped during the preparation process.
Alternatively, the sodium source is selected from Na 2 CO 3 One or more of NaOH.
Alternatively, the potassium source is selected from KOH, K 2 O、K 2 CO 3 、KHCO 3 、KNO 3 One or more of the following.
Optionally, the calcium source is selected from CaCO 3 、Ca(OH) 2 、CaC 2 O 4 、CaO、Ca(NO 3 ) 2 One or more of the following.
According to the sodium ion battery anode material provided by the invention, the precursor of the potassium source and/or the precursor of the calcium source are doped, and the doped element is used as a support column of the sodium ion layer, so that the whole phase change process of the material is prevented in the circulating process, and the stability of crystal lattices is protected; because the ionic radius of the calcium ion and the potassium ion is similar to that of the sodium ion, the difference between the calcium ion and the potassium ion and the transition metal is large, the calcium ion and the potassium ion can only enter the sodium ion layer but not enter the transition metal layer in the synthesis process, so that the stability of the positive electrode material of the sodium ion battery is greatly improved, and the cycle life of the sodium ion battery is prolonged.
Drawings
Fig. 1 is a schematic structural diagram of a positive electrode material of a sodium ion battery according to an embodiment of the present invention;
FIG. 2 shows Na according to an embodiment of the present invention 0.94 Ca 0.03 Ni 1/3 Fe 1/3 Mn 1/3 O 2 And NaNi 1/3 Fe 1/3 Mn 1/3 O 2 A capacity retention rate result graph of (2);
FIG. 3 shows Na according to an embodiment of the present invention 0.65 K 0.02 Mg 0.2 Mn 0.8 O 2 And Na (Na) 0.67 Mg 0.2 Mn 0.8 O 2 A capacity retention rate result graph of (2);
reference numerals in the drawings of the specification are as follows:
1. a transition metal layer; 2. a sodium ion layer; 3. transition metal ions; 4. sodium ions; 5. an oxygen atom.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The embodiment of the invention provides a positive electrode material of a sodium ion battery, which has the general formula: (Na) x Ca y K z )Me 1-γ O 2-σ In the general formula, x+y+z is more than or equal to 0.5 and less than or equal to 1, and the value range of x is [0.5,1 ]]The value range of y is [0,0.1 ]]The value range of z is [0,0.3]And y and z are not 0 at the same time, and the values of gamma and sigma are within the range of [ -0.3,0.3]And Me is a metal element.
The proportion of each element in the positive electrode material is controlled within a specific range, so that the positive electrode material has higher capacity performance and cycle performance.
The proportion of each element in the sodium ion layer is controlled within a specific range, so that the sodium ion layer has less chemistryComposition defects, reducing impurity phases in the material, and particularly, fully utilizing Na + And K + And/or Ca + The structural stability of the positive electrode material is improved, and the cycle performance and the capacity performance of the positive electrode material are effectively improved.
In some embodiments of the present application, the value range of x is preferably [0.6,1 ]]Further, the value range of x is preferably [0.8,1 ]]The method comprises the steps of carrying out a first treatment on the surface of the The value range of y is preferably [0,0.08 ]]Further, the value range of y is preferably [0,0.05 ]]The method comprises the steps of carrying out a first treatment on the surface of the The value range of z is preferably [0,0.1 ]]Further, the value range of z is [0,0.07 ]]. Na is made to be + 、K + 、Ca + The proportion of the catalyst is in the range, which is beneficial to improving the capacity performance and the cycle performance of the anode material.
The values of gamma and sigma are within the range of [ -0.3,0.3]. The proportion of the transition metal and oxygen in the transition metal layer is controlled within a specific range, so that the transition metal layer in the transition metal layer has fewer chemical composition defects, impurity phases in the material are reduced, and particularly, the synergistic effect of the transition metal layer and the sodium ion layer can be fully exerted, the structural stability of the positive electrode material is improved, and the cycle performance and the capacity performance of the positive electrode material are effectively improved. And gamma and sigma are correction values of transition metal and oxygen deviating from an ideal value in a molar ratio of 1:2, and the transition metal and oxygen in the transition metal layer are connected through a metal-oxygen (Me-O) bond by controlling the proportion of the transition metal and the oxygen in the transition metal layer, so that the interference of other impurities can be reduced, the structure of the positive electrode material is more stable, the damage of dissolution of transition metal ions to the positive electrode and the negative electrode is reduced, the sodium ion battery is ensured to have lower internal resistance, and the cycle performance and the capacity performance of the positive electrode material are further improved.
The positive electrode material provided herein satisfies the molecular formula (Na x Ca y K z )Me 1-γ O 2-σ The air stability of the positive electrode material can be improved by doping the electrochemical transition metal Me, the capacity loss of the positive electrode material in the charging process can be effectively reduced, and the transition metal Me in the charging and discharging processesThe electron transfer provides effective charge compensation for the deintercalation/intercalation of sodium ions, and can effectively improve the average voltage and specific capacity of the anode material; meanwhile, by doping non-sodium elements, the structural stability and capacity retention rate of the positive electrode material in the charge-discharge cycle process can be effectively improved; thereby improving the capacity performance, average voltage and cycle performance of the positive electrode material.
In some embodiments, the element in the brackets occupies a sodium ion layer, and the doped element can be Ca + And K + At least one of them.
Because the ionic radius of the calcium ion and the potassium ion is similar to that of the sodium ion, the difference between the calcium ion and the potassium ion and the transition metal is large, the calcium ion and the potassium ion can only enter the sodium ion layer but not enter the transition metal layer in the synthesis process, therefore, when the calcium ion and the potassium ion are doped in the sodium ion layer, the doped calcium ion and potassium ion are used as the support of the sodium ion layer, the whole phase change process of the material is prevented in the circulation process, the stability of crystal lattice is protected, and the cycle life of the sodium ion battery is prolonged.
In some embodiments, the Me is selected from at least one of Fe, cu, mn, ni, co, li, mg, ti, sc, V, cr, zn, Y, zr, nb, mo.
The Me is transition metal, fe, cu, mn, ni, co, li, mg, ti, sc, V, cr, zn, Y, zr, nb, mo has electrochemical properties, can improve the air stability of the positive electrode material, effectively reduces the capacity loss of the positive electrode material in the first charging process, and provides effective charge compensation for the deintercalation/intercalation of sodium ions by the electron transfer of the transition metal Me in the charging and discharging process, so that the average voltage and specific capacity of the positive electrode material can be effectively improved.
As shown in fig. 1, in some embodiments, the positive electrode material crystal is composed of a transition metal layer 1 and a sodium ion layer 2, the transition metal ions 3 occupy the transition metal layer 1, the sodium ions 4 occupy the sodium ion layer 2, the oxygen atoms 5 are located around the transition metal ions 3, and the oxygen atoms 5 are connected with the transition metal ions 3 through metal-oxygen (Me-O) bonds.
By incorporating into the positive electrode materialNa of transition metal Me and sodium ion layer + 、K + 、Ca + The proportion is controlled in a certain range, so that the Na of the transition metal Me and sodium ion layer can be better exerted + 、K + 、Ca + The cell parameter c/a is increased, and the metal-oxygen (M-O) bond is enhanced, so that the crystal structure of the positive electrode material has larger interlayer spacing, sodium ions are easier to be detached and embedded between the layers, and the charge-discharge specific capacity of the positive electrode material is improved; and simultaneously, the positive electrode material has a more stable structure and higher cycle capacity retention rate.
In some embodiments, a method of preparing a positive electrode material for a sodium ion battery includes the operations of:
preparing a sodium ion battery anode material by adopting a sodium source and a Me source through a solid phase method or a coprecipitation and solid phase method and sintering;
wherein at least one of a potassium source and a calcium source is doped during the preparation process.
Next, a method for preparing a positive electrode material of a sodium ion battery in the present application is described. According to this production method, the above positive electrode active material can be produced. The preparation method comprises coprecipitation and solid phase method;
the preparation method of the coprecipitation and solid phase method comprises the following steps:
dissolving one or more transition metals in deionized water according to a stoichiometric ratio to form a solution A; simultaneously, ammonia water B is configured according to the stoichiometric ratio; a and B are added into a continuous stirring reaction kettle at a constant speed, and meanwhile, the pH value of the solution is ensured to be 10+/-0.5; thereafter, the solid product formed in this process is dried by filtration to form precursor C.
Stoichiometric ratio of Na 2 CO 3 Mixing one or more of NaOH, a potassium precursor and/or a calcium source precursor with a proper amount of precursor C, ball-milling to form a precursor D, calcining the precursor D in a kiln, cooling and crushing to obtain the product.
The preparation of the positive electrode active material of the present application is not limited to the above-described coprecipitation+solid phase method, and a solid phase method may be simply employed. The positive electrode active material can be prepared by a person skilled in the art according to the chemical composition and structure of the positive electrode active material and the preparation steps of the solid phase method.
The preparation method of the solid phase method comprises the following steps:
and (3) weighing oxides or carbonates of Na, K, ca and Me according to a specific atomic ratio, uniformly mixing the oxides or carbonates by ball milling and the like, and sintering the mixture in a kiln with air or oxygen to obtain a final finished product material.
Wherein calcination may be carried out using methods and equipment well known in the art, for example using a muffle furnace. The temperature of calcination may be 750 ℃ to 850 ℃, for example 780 ℃ to 820 ℃, and for example 800 ℃; the calcination time may be 6 to 10 hours, for example 7 to 9 hours, and further for example 8 hours.
Finally, the elemental proportions were confirmed by ICP-OES detection while the crystal forms were confirmed by XRD.
In some embodiments, the sodium source is selected from Na 2 CO 3 One or more of NaOH.
The sodium source may be a conventional sodium source used in the art to dope sodium, preferably sodium carbonate or sodium hydroxide, or may be other sodium sources, not specifically mentioned herein.
In some embodiments, the potassium precursor is selected from KOH, K 2 O、K 2 CO 3 、KHCO 3 、KNO 3 One or more of the following. The potassium source may be a conventional potassium source used in the art for doping potassium, preferably K 2 CO 3 Or KOH.
In some embodiments, the precursor of the calcium source is selected from CaCO 3 、Ca(OH) 2 、CaC 2 O 4 、CaO、Ca(NO 3 ) 2 One or more of the following. The calcium source may be conventional calcium source used in the art for doping potassium, preferably CaCO 3 Or Ca (OH) 2 。
The ionic radius of the calcium ion and the potassium ion is similar to that of the sodium ion, the difference between the calcium ion and the potassium ion and the transition metal is large, and the calcium ion and the potassium ion only can enter the sodium ion layer but cannot enter the transition metal layer in the synthesis process, so that when the calcium ion and the potassium ion are doped in the sodium ion layer, the doped calcium ion and potassium ion serve as the support of the sodium ion layer, the integral phase change process of the material is prevented in the circulation process, the stability of crystal lattices is protected, and the cycle life of the sodium ion battery is prolonged.
Examples
The following examples more particularly describe the disclosure of the present application, which are intended as illustrative only, since numerous modifications and variations within the scope of the disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
Example 1
Preparation method of battery anode material
Weighing NiSO according to the molar ratio of 1:1:1 4 ，Fe 3 (SO 4 ) 2 ，MnSO 4 It was mixed uniformly to form a mixture a.
At normal temperature, the mixture A and deionized water are mixed according to the mass ratio of 1:10-20, and forming a solution A.
Simultaneously preparing 0.1mol/l ammonia water B; a and B are added into a continuous stirring reaction kettle at a constant speed at the same time, so that the PH value of the solution is ensured to be 10+/-0.5; the product formed in the process is filtered and dried to form precursor C.
Na is respectively weighed according to the mol ratio of 1:0.03:1 2 CO 3 ，CaCO 3 Mixing with the precursor C uniformly, putting into a ball mill for grinding to form a precursor D, sintering the precursor D in a kiln for 8 hours at 800 ℃, cooling and crushing to obtain the product.
The proportion of elements is confirmed by ICP-OES detection elements, and the molecular formula of the obtained battery anode material is as follows: na (Na) 0.94 Ca 0.03 Ni 1/3 Fe 1/3 Mn 1/3 O 2 。
At the same time confirm Na by XRD 0.94 Ca 0.03 Ni 1/3 Fe 1/3 Mn 1/3 O 2 The crystal form of the material is O 3 Structure is as follows.
O 3 The structure is two-phase layered, has electrochemical stability superior to that of a single phase, and has excellent capacity retention during long cycles.
Example 2
Similar to example 1, except that MgSO was weighed in a molar ratio of 1:4 4 With MnSO 4 It was mixed uniformly to form a mixture a.
Na is respectively weighed according to the mol ratio of 1:0.02:1 2 CO 3 ，K 2 CO 3 And a precursor C;
then, the element proportion is confirmed by ICP-OES detection, and the molecular formula of the obtained battery anode material is as follows: na (Na) 0.65 K 0.02 Mg 0.2 Mn 0.8 O 2 。
At the same time confirm Na by XRD 0.65 K 0.02 Mg 0.2 Mn 0.8 O 2 The crystal form of the material is P 2 Structure is as follows.
P 2 The structure is two-phase layered, has electrochemical stability superior to that of a single phase, and has excellent capacity retention during long cycles.
Comparative example 1
Similar to example 1, except that Na was weighed in a molar ratio of 1:1, respectively 2 CO 3 And precursor C.
Then, the element proportion is confirmed by ICP-OES detection, and the molecular formula of the obtained battery anode material is as follows: naNi 1/3 Fe 1/3 Mn 1/3 O 2 。
Comparative example 2
Similar to example 2, except that Na was weighed in a molar ratio of 1:1, respectively 2 CO 3 And precursor C.
Then, the element proportion is confirmed by ICP-OES detection, and the molecular formula of the obtained battery anode material is as follows: naNi 1/3 Fe 1/3 Mn 1/3 O 2.
Test part
(1) Capacity performance and cycle performance test of positive electrode material
Testing the battery: the battery is a soft package battery with 2 Ah;
and (3) a negative electrode: the same hard carbon is used;
positive electrode material: positive electrode materials of example 1, example 2, comparative example 1, comparative example 2, respectively;
experimental facilities: battery testing cabinet (model-SC-80-CC-3)
The experimental method comprises the following steps:
the sodium ion flexible package batteries prepared in example 1 and comparative example 1, example 2 and comparative example 2 were charged at constant current at 1C rate to a voltage of 4.0V at 25 ℃ and normal pressure (0.1 MPa), the charge capacity at this time was recorded as the first charge capacity of the flexible package battery, and the first discharge capacity was recorded as 100%; then standing for 10min, and discharging to a voltage of 1.5V at a constant current of 1C ratio, standing for 10min, wherein the discharge capacity is recorded as the first-cycle discharge specific capacity of the sodium ion battery in a cyclic charge-discharge process. And carrying out 500-circle cyclic charge and discharge test on the flexible package battery according to the method, and recording the charge specific capacity and the discharge specific capacity of each circle of cycle.
Capacity retention (%) after 500 cycles of sodium ion flexible package battery=discharge specific capacity of 500 cycles/first cycle discharge specific capacity×100%.
The results are shown in fig. 2 and 3.
As can be seen from the test results of FIG. 2, na prepared in example 1 of the present invention 0.94 Ca 0.03 Ni 1 /3Fe 1 /3Mn 1 /3O 2 3% of calcium ions are doped into the sodium layer, and during the circulation process, the sodium is compared with the NaNi prepared in the comparative example 1 1 /3Fe 1 /3Mn 1 O 2 In contrast, from the start of the experiment, the positive electrode material prepared in example 1 had a higher capacity retention than the positive electrode material prepared in comparative example 1, and the positive electrode material prepared in example 1 had a higher capacity retention than the positive electrode material prepared in comparative example 1 with the increase in the number of cyclesThe difference of the rates is larger and larger, and when the cycle number is 500, the cycle life is improved by 29.3%.
As can be seen from the test results of FIG. 3, na prepared in example 2 of the present invention 0.65 K 0.02 Mg 0.2 Mn 0.8 O 2 The Na layer was doped with 2% of potassium ion, and during the cycle, the Na layer was prepared in accordance with comparative example 2 0.67 Mg 0.2 Mn 0.8 O 2 In contrast, from the start of the experiment, the capacity retention rate of the cathode material prepared in example 2 was higher than that of the cathode material prepared in comparative example 2, and the cathode material prepared in example 2 was more and more different in capacity retention rate from that of the cathode material prepared in comparative example 2 with the increase of the number of cycles, and the cycle life was improved by 18.5% when the number of cycles was 500 cycles.
Therefore, when the sodium ion battery anode material is doped with calcium ions and potassium ions in the sodium ion layer, the doped calcium ions and potassium ions serve as struts of the sodium ion layer, so that the whole phase change process of the material is prevented in the circulating process, the stability of crystal lattices is protected, and the circulating life of the sodium ion battery is prolonged.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims (8)

1. A positive electrode material of a sodium ion battery is characterized in that: the general formula of the positive electrode material is as follows:
(Na x Ca y K z )Me 1-γ O 2-σ in the general formula, x+y+z is more than or equal to 0.5 and less than or equal to 1, and the value range of x is [0.5,1 ]]The value range of y is [0,0.1 ]]The value range of z is [0,0.3]And y and z are not 0 at the same time, and the values of gamma and sigma are within the range of [ -0.3,0.3]And Me is a metal element.
2. The sodium ion battery positive electrode material according to claim 1, wherein: the elements within the brackets occupy the sodium ion layer.
3. The sodium ion battery positive electrode material according to claim 1, wherein: the Me is at least one selected from Al and Fe, cu, mn, ni, co, li, mg, ti, sc, V, cr, zn, Y, zr, nb, mo.
4. The sodium ion battery positive electrode material according to claim 1, wherein: the positive electrode material crystal consists of a transition metal layer and a sodium ion layer, wherein transition metal ions occupy the transition metal layer, sodium ions occupy the sodium ion layer, oxygen atoms are positioned around the transition metal ions, and the oxygen atoms are connected with the transition metal ions through metal-oxygen (Me-O) bonds.
5. The method for preparing a positive electrode material for sodium ion battery according to any one of claims 1 to 4, comprising the following operations:
preparing a sodium ion battery anode material by adopting a sodium source and a Me source through a solid phase method or a coprecipitation and solid phase method and sintering;
wherein at least one of a potassium source and a calcium source is doped during the preparation process.
6. The method for preparing a positive electrode material of a sodium ion battery according to claim 5, wherein: the sodium source is selected from Na 2 CO 3 One or more of NaOH.
7. The method for preparing a positive electrode material of a sodium ion battery according to claim 5, wherein: the potassium source is selected from KOH, K 2 O、K 2 CO 3 、KHCO 3 、KNO 3 One or more of the following.
8. The method for preparing a positive electrode material of a sodium ion battery according to claim 5, wherein: the calcium source is selected from CaCO 3 、Ca(OH) 2 、CaC 2 O 4 、CaO、Ca(NO 3 ) 2 One or more of the following.
CN202211550255.6A 2022-12-05 2022-12-05 Sodium ion battery positive electrode material and preparation method thereof Pending CN116130644A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211550255.6A CN116130644A (en) 2022-12-05 2022-12-05 Sodium ion battery positive electrode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211550255.6A CN116130644A (en) 2022-12-05 2022-12-05 Sodium ion battery positive electrode material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN116130644A true CN116130644A (en) 2023-05-16

Family

ID=86298235

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211550255.6A Pending CN116130644A (en) 2022-12-05 2022-12-05 Sodium ion battery positive electrode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN116130644A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116544417A (en) * 2023-07-06 2023-08-04 宁波容百新能源科技股份有限公司 Positive electrode active material, preparation method thereof, positive electrode plate and sodium ion battery
CN117254020A (en) * 2023-11-13 2023-12-19 江门市科恒实业股份有限公司 Aluminum phosphate coated calcium-doped sodium ion battery positive electrode material and preparation method thereof
CN117756195A (en) * 2024-02-22 2024-03-26 贵州振华新材料股份有限公司 pre-sodium treated copper-zinc-based sodium ion battery positive electrode material and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116544417A (en) * 2023-07-06 2023-08-04 宁波容百新能源科技股份有限公司 Positive electrode active material, preparation method thereof, positive electrode plate and sodium ion battery
CN116544417B (en) * 2023-07-06 2024-03-19 宁波容百新能源科技股份有限公司 Positive electrode active material, preparation method thereof, positive electrode plate and sodium ion battery
CN117254020A (en) * 2023-11-13 2023-12-19 江门市科恒实业股份有限公司 Aluminum phosphate coated calcium-doped sodium ion battery positive electrode material and preparation method thereof
CN117254020B (en) * 2023-11-13 2024-03-08 江门市科恒实业股份有限公司 Aluminum phosphate coated calcium-doped sodium ion battery positive electrode material and preparation method thereof
CN117756195A (en) * 2024-02-22 2024-03-26 贵州振华新材料股份有限公司 pre-sodium treated copper-zinc-based sodium ion battery positive electrode material and preparation method thereof

Similar Documents

Publication Publication Date Title
JP4000041B2 (en) Positive electrode active material for lithium secondary battery
JP4789066B2 (en) Cathode active material for non-aqueous electrolyte secondary battery and method for producing the same
CN116130644A (en) Sodium ion battery positive electrode material and preparation method thereof
EP3444226A1 (en) Spherical or spherical-like cathode material for lithium-ion battery and lithium-ion battery
WO2017061633A1 (en) Lithium-nickel-containing composite oxide and method for producing same, and nonaqueous electrolyte secondary battery
US20160049645A1 (en) Cathode material for lithium ion secondary battery, method of producing the same, and lithium ion secondary battery
CN111762768B (en) Spinel type lithium manganate-phosphate composite cathode material and preparation method thereof
Ren et al. Modification of LiNi0. 8Co0. 1Mn0. 1O2 cathode materials from the perspective of chemical stabilization and kinetic hindrance
KR102649190B1 (en) Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same
CN110649230B (en) Nanometer rivet core-shell structure anode material and preparation method thereof
WO2024016662A1 (en) Composite coating agent for positive electrode material, high-nickel single-crystal positive electrode material, and battery
CN115207342A (en) Nickel-cobalt-manganese ternary positive electrode material with lithium-deficient and oxygen-deficient rock salt phase structure on surface layer
KR20190007801A (en) Method for producing positive electrode active material
CN111924886B (en) Lithium cobaltate cathode material with core-shell structure and preparation method thereof
CN116314731B (en) Sodium ion battery anode material, precursor thereof, preparation method and application
CN111370666A (en) Positive electrode material, preparation method and application thereof
CN116093303A (en) Sodium-lanthanum co-doped modified lithium-rich manganese-based positive electrode material and preparation method thereof
CN115881943A (en) Lithium-rich cathode material, preparation method thereof and lithium ion battery
CN116190631A (en) Lithium-rich manganese-based positive electrode active material and battery
CN116454267A (en) Sodium-electricity layered oxide and preparation method thereof
CN114300664B (en) Lithium-rich single crystal positive electrode material with surface coated with lithium selenate, and preparation method and application thereof
CN114927682A (en) LiNi ternary material for increasing high nickel content x Co y Mn 1-x-y O 2 Method for cycling stability and safety of anode material
CN113562779A (en) Single crystal NCM ternary material coated with lithium aluminum zirconate in situ
KR20220118497A (en) Positive active material and lithium secondary battery comprising same
KR102502591B1 (en) Cathode active material, and lithium ion battery including the same

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