CN109449395A - A kind of preparation method of lithium ion conductor coating modification sodium-ion battery positive material - Google Patents
A kind of preparation method of lithium ion conductor coating modification sodium-ion battery positive material Download PDFInfo
- Publication number
- CN109449395A CN109449395A CN201811223499.7A CN201811223499A CN109449395A CN 109449395 A CN109449395 A CN 109449395A CN 201811223499 A CN201811223499 A CN 201811223499A CN 109449395 A CN109449395 A CN 109449395A
- Authority
- CN
- China
- Prior art keywords
- sodium
- solution
- positive material
- hours
- ion battery
- 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
Links
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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of preparation methods of lithium ion conductor coating modification sodium-ion battery positive material, belong to technical field of inorganic material.The method of the present invention has prepared the sodium-ion battery positive material of pure phase lithium ion conductor cladding by sol-gal process and wet-chemical cladding process.The method of the present invention synthesis technology is simple, and high production efficiency is suitable for scale production.In addition, the advantages that raw material required for the method for the present invention reactant is easy to get, is nontoxic, is low in cost, and production process is not necessarily to special protection, and preparation method is convenient, and yield is larger, and operability is good, and repeatability is stronger.The sodium-ion battery positive material of the lithium ion conductor cladding of the method for the present invention preparation has large increase and improvement in terms of the battery performances such as battery specific capacity and multiplying power compared to the material not coated.
Description
Technical field
The present invention relates to a kind of preparation methods of lithium ion conductor coating modification sodium-ion battery positive material, more particularly to
Lithium ion conductor (Li2SiO3、Li2TiO3、Li2ZrO3、Li2SnO3) the new preparation side of cladding sodium-ion battery positive material
Method belongs to technical field of inorganic material.
Background technique
With resource scarcity, energy shortage and the pollution problem got worse, the exploitation of new energy is increasingly by people
Favor.By the development of many decades, lithium ion battery has become a kind of energy of universal high effective portable, and answers extensively
For fields such as mobile phone, wireless telecommunications, electric cars, but since the content of sodium in nature is significantly larger than the content of lithium, and
Sodium-ion battery is at low cost compared with lithium ion battery and easily prepares, and sodium-ion battery is also considered as that most have can in future
A kind of novel battery of lithium ion battery can be substituted.The practical major obstacle of restricting current sodium-ion battery is just the absence of can
Stable, embedding sodium ion long-life type electrode material.In existing sodium-ion battery positive material, the transition of layer structure
Metal oxide cathode material has been widely recognized, and is possible to extensive and realizes commercialization, but that there are capacity is low, times
The disadvantages of rate performance is poor.Therefore existing many problems all limit the development of sodium-ion battery, but for sodium-ion battery
Study on the modification still has very big scientific research value.The modified method of sodium-ion battery positive material mainly has doping at present
The transition metal element of such as Co, Ni, Cu, Zn, Mg, Ti or the like pass through some such as Al of cladding2O3, MgO etc. oxidation
Object.
Summary of the invention
The purpose of the present invention is to propose to a kind of preparation method of lithium ion conductor coating modification sodium-ion battery positive material,
By carrying out lithium ion conductor cladding to sodium-ion battery positive material, improve the chemical property of sodium-ion battery positive material
(cycle performance, high rate performance etc.), and make the preparation process simple process, low in cost of material, it is easy to large-scale production.
The preparation method of lithium ion conductor coating modification sodium-ion battery positive material proposed by the present invention, including following step
It is rapid:
(1) 3-5g ethylene glycol and 4-5g citric acid are mixed and is dissolved in deionized water, be stirred to obtain under room temperature
One solution, wherein the concentration of ethylene glycol and citric acid is respectively 0.06-0.1g/mL；0.08-0.1g/mL, by sodium acetate, acetic acid
Manganese and ferric nitrate are separately added into the first solution, stir to get wet colloidal sol, and wherein sodium acetate, manganese acetate and ferric nitrate are molten first
Molar concentration in liquid is respectively 0.134mol/L, 0.1-0.16mol/L, 0.04-0.1mol/L；
(2) wet gel that step (1) obtains successively is subjected to aging, drying, pre-sintering and high temperature sintering, wherein aging temperature
Degree is 80-100 DEG C, and the time is 5-10 hour；Drying temperature is 120-150 DEG C, and the time is 18-24 hour；Pre-burning junction temperature
Degree is 500 DEG C, and the pre-sintering time is 5 hours；High temperature sintering temperature is 800 DEG C -1000 DEG C, and the time is 12 hours；Finally
It is cooled down rapidly under conditions of anhydrous and oxygen-free, obtains sodium-ion battery positive material Na0.67MnxFe1-xO2, wherein 0.5≤x≤
0.8；
(3) lithium acetate and Ester are mixed, obtain mixture, the molar ratio of lithium salts and esters is 2 in mixture:
1, in ethanol by mixture dissolution, the second solution is obtained, so that lithium acetate molar concentration in the second solution is 0.011-
0.22mol/L；The sodium-ion battery positive material that step (2) obtains is added in the second solution, so that sodium ion in liquor
Cell positive material concentration is 25g/L, obtains third solution, obtained third solution is stirred 5-10 hour at normal temperature,
Then 80 DEG C of -100 DEG C of baking ovens drying, drying time are 10-12 hour, obtain solid-oxide, solid-oxide is ground
At being sintered after powder, with 2 DEG C -5 DEG C heating rates per minute, 500 DEG C of 5-10 hours of -600 DEG C of heat preservations are raised to, finally
It is cooled down rapidly under conditions of anhydrous and oxygen-free, obtains the sodium-ion battery positive material of lithium ion conductor cladding.
Ester in above-mentioned preparation method can be tetraethyl orthosilicate, butyl titanate, tetrabutyl zirconate or four
Butyl tin.
A kind of preparation method of lithium ion conductor coating modification sodium-ion battery positive material proposed by the present invention, advantage
It is:
The method of the present invention has prepared pure phase lithium ion conductor packet by simple sol-gal process and wet-chemical cladding process
The sodium-ion battery positive material covered.The method of the present invention synthesis technology is simple, and high production efficiency is suitable for scale production.In addition,
Raw material required for the method for the present invention reactant is easy to get, is nontoxic, is low in cost, and production process is not necessarily to special protection, preparation method
The advantages that convenient, yield is larger, and operability is good, and repeatability is stronger.The sodium of the lithium ion conductor cladding of the method for the present invention preparation
Ion battery positive electrode has very in terms of the battery performances such as battery specific capacity and multiplying power compared to the material not coated
It is big to improve and improve.
Detailed description of the invention
Fig. 1 is the sodium-ion battery positive material (Li of lithium ion conductor cladding prepared by the embodiment of the present invention 12SiO3@
Na0.67Mn0.5Fe0.5O2) X-ray diffractogram (XRD).
Fig. 2 is the sodium-ion battery positive material (Li of lithium ion conductor cladding prepared by the embodiment of the present invention 12SiO3@
Na0.67Mn0.5Fe0.5O2) TEM map.
Fig. 3 is the sodium-ion battery positive material (Li of lithium ion conductor cladding prepared by the embodiment of the present invention 12SiO3@
Na0.67Mn0.5Fe0.5O2) and uncoated sodium-ion battery positive material (Na0.67Mn0.5Fe0.5O2) 0.1C (1C=200mAh/
G) specific discharge capacity recycles comparison diagram.
Fig. 4 is the sodium-ion battery positive material (Li of lithium ion conductor cladding prepared by the embodiment of the present invention 12SiO3@
Na0.67Mn0.5Fe0.5O2) and uncoated sodium-ion battery positive material (Na0.67Mn0.5Fe0.5O2) putting under different multiplying
Electric specific capacity recycles comparison diagram.
Specific embodiment
The preparation method of lithium ion conductor coating modification sodium-ion battery positive material proposed by the present invention, including following step
It is rapid:
(1) 3-5g ethylene glycol and 4-5g citric acid are mixed and is dissolved in deionized water, be stirred to obtain under room temperature
One solution, wherein the concentration of ethylene glycol and citric acid is respectively 0.06-0.1g/mL；0.08-0.1g/mL, by sodium acetate, acetic acid
Manganese and ferric nitrate are separately added into the first solution, stir to get wet colloidal sol, and wherein sodium acetate, manganese acetate and ferric nitrate are molten first
Molar concentration in liquid is respectively 0.134mol/L, 0.1-0.16mol/L, 0.04-0.1mol/L；
(2) wet gel that step (1) obtains successively is subjected to aging, drying, pre-sintering and high temperature sintering, wherein aging temperature
Degree is 80-100 DEG C, and the time is 5-10 hour；Drying temperature is 120-150 DEG C, and the time is 18-24 hour；Pre-burning junction temperature
Degree is 500 DEG C, and the pre-sintering time is 5 hours；High temperature sintering temperature is 800 DEG C -1000 DEG C, and the time is 12 hours；Finally
It is cooled down rapidly under conditions of anhydrous and oxygen-free, obtains sodium-ion battery positive material Na0.67MnxFe1-xO2, wherein 0.5≤x≤
0.8；
(3) lithium acetate and Ester are mixed, obtain mixture, the molar ratio of lithium salts and esters is 2 in mixture:
1, in ethanol by mixture dissolution, the second solution is obtained, so that lithium acetate molar concentration in the second solution is 0.011-
0.22mol/L；The sodium-ion battery positive material that step (2) obtains is added in the second solution, so that sodium ion in liquor
Cell positive material concentration is 25g/L, obtains third solution, obtained third solution is stirred 5-10 hour at normal temperature,
Then 80 DEG C of -100 DEG C of baking ovens drying, drying time are 10-12 hour, obtain solid-oxide, solid-oxide is ground
At being sintered after powder, with 2 DEG C -5 DEG C heating rates per minute, 500 DEG C of 5-10 hours of -600 DEG C of heat preservations are raised to, finally
It is cooled down rapidly under conditions of anhydrous and oxygen-free, obtains the sodium-ion battery positive material of lithium ion conductor cladding.
Ester in above-mentioned preparation method, the tetraethyl orthosilicate that can be positive, butyl titanate, tetrabutyl zirconate or
Tetrabutyltin.
The embodiment of the method for the present invention is described below:
Embodiment one:
(1) 3.2084g ethylene glycol and 4.1463g citric acid are mixed and is dissolved in deionized water, is stirred under room temperature
The first solution is obtained, wherein the concentration of ethylene glycol and citric acid is respectively 0.064g/mL；0.0829g/mL, by sodium acetate, acetic acid
Manganese and ferric nitrate are separately added into the first solution, stir to get wet colloidal sol, and wherein sodium acetate, manganese acetate and ferric nitrate are molten first
Molar concentration in liquid is respectively 0.134mol/L, 0.1mol/L, 0.1mol/L；
(2) wet gel that step (1) obtains successively is subjected to aging, drying, pre-sintering and high temperature sintering, wherein aging temperature
Degree is 80 DEG C, and the time is 5 hours；Drying temperature is 150 DEG C, and the time is 24 hours；Pre-sintering temperature is 500 DEG C, pre-burning
The knot time is 5 hours；High temperature sintering temperature is 900 DEG C, and the time is 12 hours；It is cooled down rapidly under conditions of anhydrous and oxygen-free
Obtain sodium-ion battery positive material Na0.67Mn0.5Fe0.5O2；
(3) lithium acetate and tetraethyl orthosilicate are mixed, obtains mixture, the molar ratio of lithium salts and esters in mixture
In ethanol by mixture dissolution the second solution is obtained, so that lithium acetate molar concentration in the second solution is for 2:1
0.011mol/L；The sodium-ion battery positive material that step (2) obtains is added in the second solution, wherein sodium ion in liquor
Cell positive material concentration is 25g/L, obtains third solution.Obtained third solution is stirred into 5 hours at normal temperature, then
The drying of 80 DEG C of baking ovens, time are 10 hours, obtain solid-oxide, solid-oxide are pulverized last sintering, with 2 DEG C
Heating rate per minute is raised to 600 DEG C of 5 hours of heat preservation, is placed under conditions of anhydrous and oxygen-free and cools down rapidly, obtains lithium ion
Sodium-ion battery positive material (the Li of conductor cladding2SiO3@Na0.67Mn0.5Fe0.5O2)。
Gained lithium ion conductor coats sodium-ion battery positive material characterization: the sodium ion electricity of gained lithium ion conductor cladding
Pond positive electrode (Li2SiO3@Na0.67Mn0.5Fe0.5O2) pass through the solid solution that X-ray diffractometer analysis can must be pure phase, such as Fig. 1
It is shown.Fig. 2 is the sodium-ion battery positive material (Li of the present embodiment lithium ion conductor cladding2SiO3@Na0.67Mn0.5Fe0.5O2)
TEM map, it was demonstrated that one layer of Li formd on positive electrode surface really by the method for this wet-chemical2SiO3.Fig. 3 is
Sodium-ion battery positive material (the Li of the cladding of lithium ion conductor obtained by the present embodiment2SiO3@Na0.67Mn0.5Fe0.5O2) with do not wrap
Sodium-ion battery positive material (the Na covered0.67Mn0.5Fe0.5O2) the capacity circulating comparison diagram under 0.1C discharge current density.Fig. 4
It is the sodium-ion battery positive material (Li of the cladding of lithium ion conductor obtained by the present embodiment2SiO3@Na0.67Mn0.5Fe0.5O2) and not
Sodium-ion battery positive material (the Na of cladding0.67Mn0.5Fe0.5O2) respectively in 0.05C, 0.1C, 0.2C, 0.5C, 1C, 2C and 5C
Specific capacity comparison diagram under (1C=200mAh/g) discharge current density.
Embodiment two:
(1) 3.2084g ethylene glycol and 4.1463g citric acid are mixed and is dissolved in deionized water, is stirred under room temperature
The first solution is obtained, wherein the concentration of ethylene glycol and citric acid is respectively 0.064g/mL；0.0829g/mL, by sodium acetate, acetic acid
Manganese and ferric nitrate are separately added into the first solution, stir to get wet colloidal sol, and wherein sodium acetate, manganese acetate and ferric nitrate are molten first
Molar concentration in liquid is respectively 0.134mol/L, 0.1mol/L, 0.1mol/L；
(2) wet gel that step (1) obtains successively is subjected to aging, drying, pre-sintering and high temperature sintering, wherein aging temperature
Degree is 80 DEG C, and the time is 5 hours；Drying temperature is 150 DEG C, and the time is 24 hours；Pre-sintering temperature is 500 DEG C, pre-burning
The knot time is 5 hours；High temperature sintering temperature is 900 DEG C, and the time is 12 hours；It is cooled down rapidly under conditions of anhydrous and oxygen-free
Obtain sodium-ion battery positive material Na0.67Mn0.5Fe0.5O2；
(3) lithium acetate and tetraethyl orthosilicate are mixed, obtains mixture, the molar ratio of lithium salts and esters in mixture
In ethanol by mixture dissolution the second solution is obtained, so that lithium acetate molar concentration in the second solution is for 2:1
0.0165mol/L；The sodium-ion battery positive material that step (2) obtains is added in the second solution, wherein in solution sodium from
Sub- cell positive material concentration is 25g/L, obtains third solution.Obtained third solution is stirred into 5 hours at normal temperature, so
80 DEG C of baking ovens drying afterwards, time are 10 hours, obtain solid-oxide, solid-oxide are pulverized last sintering, with 2
DEG C heating rate per minute, is raised to 600 DEG C of 5 hours of heat preservation, is placed under conditions of anhydrous and oxygen-free and cools down rapidly, obtain lithium from
Sodium-ion battery positive material (the Li of sub- conductor cladding2SiO3@Na0.67Mn0.5Fe0.5O2)。
Embodiment three:
(1) 3.2084g ethylene glycol and 4.1463g citric acid are mixed and is dissolved in deionized water, is stirred under room temperature
The first solution is obtained, wherein the concentration of ethylene glycol and citric acid is respectively 0.064g/mL；0.0829g/mL, by sodium acetate, acetic acid
Manganese and ferric nitrate are separately added into the first solution, stir to get wet colloidal sol, and wherein sodium acetate, manganese acetate and ferric nitrate are molten first
Molar concentration in liquid is respectively 0.134mol/L, 0.1mol/L, 0.1mol/L；
(2) wet gel that step (1) obtains successively is subjected to aging, drying, pre-sintering and high temperature sintering, wherein aging temperature
Degree is 80 DEG C, and the time is 5 hours；Drying temperature is 150 DEG C, and the time is 24 hours；Pre-sintering temperature is 500 DEG C, pre-burning
The knot time is 5 hours；High temperature sintering temperature is 900 DEG C, and the time is 12 hours；It is cooled down rapidly under conditions of anhydrous and oxygen-free
Obtain sodium-ion battery positive material Na0.67Mn0.5Fe0.5O2；
(3) lithium acetate and tetraethyl orthosilicate are mixed, obtains mixture, the molar ratio of lithium salts and esters in mixture
In ethanol by mixture dissolution the second solution is obtained, so that lithium acetate molar concentration in the second solution is for 2:1
0.022mol/L；The sodium-ion battery positive material that step (2) obtains is added in the second solution, wherein sodium ion in liquor
Cell positive material concentration is 25g/L, obtains third solution.Obtained third solution is stirred into 5 hours at normal temperature, then
The drying of 80 DEG C of baking ovens, time are 10 hours, obtain solid-oxide, solid-oxide are pulverized last sintering, with 2 DEG C
Heating rate per minute is raised to 600 DEG C of 5 hours of heat preservation, is placed under conditions of anhydrous and oxygen-free and cools down rapidly, obtains lithium ion
Sodium-ion battery positive material (the Li of conductor cladding2SiO3@Na0.67Mn0.5Fe0.5O2)。
Example IV:
(1) 3.2084g ethylene glycol and 4.1463g citric acid are mixed and is dissolved in deionized water, is stirred under room temperature
The first solution is obtained, wherein the concentration of ethylene glycol and citric acid is respectively 0.064g/mL；0.0829g/mL, by sodium acetate, acetic acid
Manganese and ferric nitrate are separately added into the first solution, stir to get wet colloidal sol, and wherein sodium acetate, manganese acetate and ferric nitrate are molten first
Molar concentration in liquid is respectively 0.134mol/L, 0.1mol/L, 0.1mol/L；
(2) wet gel that step (1) obtains successively is subjected to aging, drying, pre-sintering and high temperature sintering, wherein aging temperature
Degree is 80 DEG C, and the time is 5 hours；Drying temperature is 150 DEG C, and the time is 24 hours；Pre-sintering temperature is 500 DEG C, pre-burning
The knot time is 5 hours；High temperature sintering temperature is 900 DEG C, and the time is 12 hours；It is cooled down rapidly under conditions of anhydrous and oxygen-free
Obtain sodium-ion battery positive material Na0.67Mn0.5Fe0.5O2；
(3) lithium acetate and tetraethyl orthosilicate are mixed, obtains mixture, the molar ratio of lithium salts and esters in mixture
In ethanol by mixture dissolution the second solution is obtained, so that lithium acetate molar concentration in the second solution is for 2:1
0.011mol/L；The sodium-ion battery positive material that step (2) obtains is added in the second solution, wherein sodium ion in liquor
Cell positive material concentration is 25g/L, obtains third solution.Obtained third solution is stirred into 5 hours at normal temperature, then
The drying of 80 DEG C of baking ovens, time are 10 hours, obtain solid-oxide, solid-oxide are pulverized last sintering, with 2 DEG C
Heating rate per minute is raised to 500 DEG C of 5 hours of heat preservation, is placed under conditions of anhydrous and oxygen-free and cools down rapidly, obtains lithium ion
Sodium-ion battery positive material (the Li of conductor cladding2SiO3@Na0.67Mn0.5Fe0.5O2)。
Embodiment five:
(1) 3.2084g ethylene glycol and 4.1463g citric acid are mixed and is dissolved in deionized water, is stirred under room temperature
The first solution is obtained, wherein the concentration of ethylene glycol and citric acid is respectively 0.064g/mL；0.0829g/mL, by sodium acetate, acetic acid
Manganese and ferric nitrate are separately added into the first solution, stir to get wet colloidal sol, and wherein sodium acetate, manganese acetate and ferric nitrate are molten first
Molar concentration in liquid is respectively 0.134mol/L, 0.1mol/L, 0.1mol/L；
(2) wet gel that step (1) obtains successively is subjected to aging, drying, pre-sintering and high temperature sintering, wherein aging temperature
Degree is 80 DEG C, and the time is 5 hours；Drying temperature is 150 DEG C, and the time is 24 hours；Pre-sintering temperature is 500 DEG C, pre-burning
The knot time is 5 hours；High temperature sintering temperature is 900 DEG C, and the time is 12 hours；It is cooled down rapidly under conditions of anhydrous and oxygen-free
Obtain sodium-ion battery positive material Na0.67Mn0.5Fe0.5O2；
(3) lithium acetate and tetraethyl orthosilicate are mixed, obtains mixture, the molar ratio of lithium salts and esters in mixture
In ethanol by mixture dissolution the second solution is obtained, so that lithium acetate molar concentration in the second solution is for 2:1
0.011mol/L；The sodium-ion battery positive material that step (2) obtains is added in the second solution, wherein sodium ion in liquor
Cell positive material concentration is 25g/L, obtains third solution.Obtained third solution is stirred into 5 hours at normal temperature, then
The drying of 80 DEG C of baking ovens, time are 10 hours, obtain solid-oxide, solid-oxide are pulverized last sintering, with 2 DEG C
Heating rate per minute is raised to 550 DEG C of 5 hours of heat preservation, is placed under conditions of anhydrous and oxygen-free and cools down rapidly, obtains lithium ion
Sodium-ion battery positive material (the Li of conductor cladding2SiO3@Na0.67Mn0.5Fe0.5O2)。
Embodiment six:
(1) 3.2084g ethylene glycol and 4.1463g citric acid are mixed and is dissolved in deionized water, is stirred under room temperature
The first solution is obtained, wherein the concentration of ethylene glycol and citric acid is respectively 0.064g/mL；0.0829g/mL, by sodium acetate, acetic acid
Manganese and ferric nitrate are separately added into the first solution, stir to get wet colloidal sol, and wherein sodium acetate, manganese acetate and ferric nitrate are molten first
Molar concentration in liquid is respectively 0.134mol/L, 0.1mol/L, 0.1mol/L；
(2) wet gel that step (1) obtains successively is subjected to aging, drying, pre-sintering and high temperature sintering, wherein aging temperature
Degree is 80 DEG C, and the time is 5 hours；Drying temperature is 150 DEG C, and the time is 24 hours；Pre-sintering temperature is 500 DEG C, pre-burning
The knot time is 5 hours；High temperature sintering temperature is 900 DEG C, and the time is 12 hours；It is cooled down rapidly under conditions of anhydrous and oxygen-free
Obtain sodium-ion battery positive material Na0.67Mn0.5Fe0.5O2；
(3) lithium acetate and butyl titanate are mixed, obtains mixture, the molar ratio of lithium salts and esters is in mixture
2:1 in ethanol by mixture dissolution obtains the second solution, so that lithium acetate molar concentration in the second solution is
0.011mol/L；The sodium-ion battery positive material that step (2) obtains is added in the second solution, wherein sodium ion in liquor
Cell positive material concentration is 25g/L, obtains third solution.Obtained third solution is stirred into 5 hours at normal temperature, then
The drying of 80 DEG C of baking ovens, time are 10 hours, obtain solid-oxide, solid-oxide are pulverized last sintering, with 2 DEG C
Heating rate per minute is raised to 600 DEG C of 5 hours of heat preservation, is placed under conditions of anhydrous and oxygen-free and cools down rapidly, obtains lithium ion
Sodium-ion battery positive material (the Li of conductor cladding2TiO3@Na0.67Mn0.5Fe0.5O2)。
Embodiment seven:
(1) 3.2084g ethylene glycol and 4.1463g citric acid are mixed and is dissolved in deionized water, is stirred under room temperature
The first solution is obtained, wherein the concentration of ethylene glycol and citric acid is respectively 0.064g/mL；0.0829g/mL, by sodium acetate, acetic acid
Manganese and ferric nitrate are separately added into the first solution, stir to get wet colloidal sol, and wherein sodium acetate, manganese acetate and ferric nitrate are molten first
Molar concentration in liquid is respectively 0.134mol/L, 0.1mol/L, 0.1mol/L；
(2) wet gel that step (1) obtains successively is subjected to aging, drying, pre-sintering and high temperature sintering, wherein aging temperature
Degree is 80 DEG C, and the time is 5 hours；Drying temperature is 150 DEG C, and the time is 24 hours；Pre-sintering temperature is 500 DEG C, pre-burning
The knot time is 5 hours；High temperature sintering temperature is 900 DEG C, and the time is 12 hours；It is cooled down rapidly under conditions of anhydrous and oxygen-free
Obtain sodium-ion battery positive material Na0.67Mn0.5Fe0.5O2；
(3) lithium acetate and tetrabutyl zirconate are mixed, obtains mixture, the molar ratio of lithium salts and esters is in mixture
2:1 in ethanol by mixture dissolution obtains the second solution, so that lithium acetate molar concentration in the second solution is
0.011mol/L；The sodium-ion battery positive material that step (2) obtains is added in the second solution, wherein sodium ion in liquor
Cell positive material concentration is 25g/L, obtains third solution.Obtained third solution is stirred into 5 hours at normal temperature, then
The drying of 80 DEG C of baking ovens, time are 10 hours, obtain solid-oxide, solid-oxide are pulverized last sintering, with 2 DEG C
Heating rate per minute is raised to 600 DEG C of 5 hours of heat preservation, is placed under conditions of anhydrous and oxygen-free and cools down rapidly, obtains lithium ion
Sodium-ion battery positive material (the Li of conductor cladding2ZrO3@Na0.67Mn0.5Fe0.5O2)。
Embodiment eight:
(1) 3.2084g ethylene glycol and 4.1463g citric acid are mixed and is dissolved in deionized water, is stirred under room temperature
The first solution is obtained, wherein the concentration of ethylene glycol and citric acid is respectively 0.064g/mL；0.0829g/mL, by sodium acetate, acetic acid
Manganese and ferric nitrate are separately added into the first solution, stir to get wet colloidal sol, and wherein sodium acetate, manganese acetate and ferric nitrate are molten first
Molar concentration in liquid is respectively 0.134mol/L, 0.1mol/L, 0.1mol/L；
(2) wet gel that step (1) obtains successively is subjected to aging, drying, pre-sintering and high temperature sintering, wherein aging temperature
Degree is 80 DEG C, and the time is 5 hours；Drying temperature is 150 DEG C, and the time is 24 hours；Pre-sintering temperature is 500 DEG C, pre-burning
The knot time is 5 hours；High temperature sintering temperature is 900 DEG C, and the time is 12 hours；It is cooled down rapidly under conditions of anhydrous and oxygen-free
Obtain sodium-ion battery positive material Na0.67Mn0.5Fe0.5O2；
(3) lithium acetate and tetrabutyltin are mixed, obtain mixture, the molar ratio of lithium salts and esters is 2 in mixture:
1, in ethanol by mixture dissolution, the second solution is obtained, so that lithium acetate molar concentration in the second solution is
0.011mol/L；The sodium-ion battery positive material that step (2) obtains is added in the second solution, wherein sodium ion in liquor
Cell positive material concentration is 25g/L, obtains third solution.Obtained third solution is stirred into 5 hours at normal temperature, then
The drying of 80 DEG C of baking ovens, time are 10 hours, obtain solid-oxide, solid-oxide are pulverized last sintering, with 2 DEG C
Heating rate per minute is raised to 600 DEG C of 5 hours of heat preservation, is placed under conditions of anhydrous and oxygen-free and cools down rapidly, obtains lithium ion
Sodium-ion battery positive material (the Li of conductor cladding2SnO3@Na0.67Mn0.5Fe0.5O2)。
Embodiment nine:
(1) 3.2084g ethylene glycol and 4.1463g citric acid are mixed and is dissolved in deionized water, is stirred under room temperature
The first solution is obtained, wherein the concentration of ethylene glycol and citric acid is respectively 0.064g/mL；0.0829g/mL, by sodium acetate, acetic acid
Manganese and ferric nitrate are separately added into the first solution, stir to get wet colloidal sol, and wherein sodium acetate, manganese acetate and ferric nitrate are molten first
Molar concentration in liquid is respectively 0.134mol/L, 0.1mol/L, 0.1mol/L；
(2) wet gel that step (1) obtains successively is subjected to aging, drying, pre-sintering and high temperature sintering, wherein aging temperature
Degree is 80 DEG C, and the time is 5 hours；Drying temperature is 150 DEG C, and the time is 24 hours；Pre-sintering temperature is 500 DEG C, pre-burning
The knot time is 5 hours；High temperature sintering temperature is 900 DEG C, and the time is 12 hours；It is cooled down rapidly under conditions of anhydrous and oxygen-free
Obtain sodium-ion battery positive material Na0.67Mn0.5Fe0.5O2；
(3) lithium acetate and tetraethyl orthosilicate are mixed, obtains mixture, the molar ratio of lithium salts and esters in mixture
In ethanol by mixture dissolution the second solution is obtained, so that lithium acetate molar concentration in the second solution is for 2:1
0.011mol/L；The sodium-ion battery positive material that step (2) obtains is added in the second solution, wherein sodium ion in liquor
Cell positive material concentration is 25g/L, obtains third solution.Obtained third solution is stirred into 5 hours at normal temperature, then
The drying of 80 DEG C of baking ovens, time are 10 hours, obtain solid-oxide, solid-oxide are pulverized last sintering, with 4 DEG C
Heating rate per minute is raised to 600 DEG C of 5 hours of heat preservation, is placed under conditions of anhydrous and oxygen-free and cools down rapidly, obtains lithium ion
Sodium-ion battery positive material (the Li of conductor cladding2SiO3@Na0.67Mn0.5Fe0.5O2)。
Embodiment ten:
(1) 3.2084g ethylene glycol and 4.1463g citric acid are mixed and is dissolved in deionized water, is stirred under room temperature
The first solution is obtained, wherein the concentration of ethylene glycol and citric acid is respectively 0.064g/mL；0.0829g/mL, by sodium acetate, acetic acid
Manganese and ferric nitrate are separately added into the first solution, stir to get wet colloidal sol, and wherein sodium acetate, manganese acetate and ferric nitrate are molten first
Molar concentration in liquid is respectively 0.134mol/L, 0.1mol/L, 0.1mol/L；
(2) wet gel that step (1) obtains successively is subjected to aging, drying, pre-sintering and high temperature sintering, wherein aging temperature
Degree is 80 DEG C, and the time is 5 hours；Drying temperature is 150 DEG C, and the time is 24 hours；Pre-sintering temperature is 500 DEG C, pre-burning
The knot time is 5 hours；High temperature sintering temperature is 900 DEG C, and the time is 12 hours；It is cooled down rapidly under conditions of anhydrous and oxygen-free
Obtain sodium-ion battery positive material Na0.67Mn0.5Fe0.5O2；
(3) lithium acetate and tetraethyl orthosilicate are mixed, obtains mixture, the molar ratio of lithium salts and esters in mixture
In ethanol by mixture dissolution the second solution is obtained, so that lithium acetate molar concentration in the second solution is for 2:1
0.011mol/L；The sodium-ion battery positive material that step (2) obtains is added in the second solution, wherein sodium ion in liquor
Cell positive material concentration is 25g/L, obtains third solution.Obtained third solution is stirred into 5 hours at normal temperature, then
The drying of 80 DEG C of baking ovens, time are 10 hours, obtain solid-oxide, solid-oxide are pulverized last sintering, with 2 DEG C
Heating rate per minute is raised to 600 DEG C of 10 hours of heat preservation, is placed under conditions of anhydrous and oxygen-free and cools down rapidly, obtain lithium from
Sodium-ion battery positive material (the Li of sub- conductor cladding2SiO3@Na0.67Mn0.5Fe0.5O2)。
Embodiment 11:
(1) 3.2084g ethylene glycol and 4.1463g citric acid are mixed and is dissolved in deionized water, is stirred under room temperature
The first solution is obtained, wherein the concentration of ethylene glycol and citric acid is respectively 0.064g/mL；0.0829g/mL, by sodium acetate, acetic acid
Manganese and ferric nitrate are separately added into the first solution, stir to get wet colloidal sol, and wherein sodium acetate, manganese acetate and ferric nitrate are molten first
Molar concentration in liquid is respectively 0.134mol/L, 0.1mol/L, 0.1mol/L；
(2) wet gel that step (1) obtains successively is subjected to aging, drying, pre-sintering and high temperature sintering, wherein aging temperature
Degree is 80 DEG C, and the time is 5 hours；Drying temperature is 150 DEG C, and the time is 24 hours；Pre-sintering temperature is 500 DEG C, pre-burning
The knot time is 5 hours；High temperature sintering temperature is 900 DEG C, and the time is 12 hours；It is cooled down rapidly under conditions of anhydrous and oxygen-free
Obtain sodium-ion battery positive material Na0.67Mn0.5Fe0.5O2；
(3) lithium acetate and tetraethyl orthosilicate are mixed, obtains mixture, the molar ratio of lithium salts and esters in mixture
In ethanol by mixture dissolution the second solution is obtained, so that lithium acetate molar concentration in the second solution is for 2:1
0.011mol/L；The sodium-ion battery positive material that step (2) obtains is added in the second solution, wherein sodium ion in liquor
Cell positive material concentration is 25g/L, obtains third solution.Obtained third solution is stirred into 5 hours at normal temperature, then
The drying of 80 DEG C of baking ovens, time are 10 hours, obtain solid-oxide, solid-oxide are pulverized last sintering, with 4 DEG C
Heating rate per minute is raised to 600 DEG C of 10 hours of heat preservation, is placed under conditions of anhydrous and oxygen-free and cools down rapidly, obtain lithium from
Sodium-ion battery positive material (the Li of sub- conductor cladding2SiO3@Na0.67Mn0.5Fe0.5O2)。
Embodiment 12:
(1) 3.2084g ethylene glycol and 4.1463g citric acid are mixed and is dissolved in deionized water, is stirred under room temperature
The first solution is obtained, wherein the concentration of ethylene glycol and citric acid is respectively 0.064g/mL；0.0829g/mL, by sodium acetate, acetic acid
Manganese and ferric nitrate are separately added into the first solution, stir to get wet colloidal sol, and wherein sodium acetate, manganese acetate and ferric nitrate are molten first
Molar concentration in liquid is respectively 0.134mol/L, 0.1mol/L, 0.1mol/L；
(2) wet gel that step (1) obtains successively is subjected to aging, drying, pre-sintering and high temperature sintering, wherein aging temperature
Degree is 80 DEG C, and the time is 5 hours；Drying temperature is 150 DEG C, and the time is 24 hours；Pre-sintering temperature is 500 DEG C, pre-burning
The knot time is 5 hours；High temperature sintering temperature is 900 DEG C, and the time is 12 hours；It is cooled down rapidly under conditions of anhydrous and oxygen-free
Obtain sodium-ion battery positive material Na0.67Mn0.5Fe0.5O2；
(3) lithium acetate and tetraethyl orthosilicate are mixed, obtains mixture, the molar ratio of lithium salts and esters in mixture
In ethanol by mixture dissolution the second solution is obtained, so that lithium acetate molar concentration in the second solution is for 2:1
0.011mol/L；The sodium-ion battery positive material that step (2) obtains is added in the second solution, wherein sodium ion in liquor
Cell positive material concentration is 25g/L, obtains third solution.Obtained third solution is stirred into 5 hours at normal temperature, then
The drying of 80 DEG C of baking ovens, time are 10 hours, obtain solid-oxide, solid-oxide are pulverized last sintering, with 5 DEG C
Heating rate per minute is raised to 600 DEG C of 5 hours of heat preservation, is placed under conditions of anhydrous and oxygen-free and cools down rapidly, obtains lithium ion
Sodium-ion battery positive material (the Li of conductor cladding2SiO3@Na0.67Mn0.5Fe0.5O2)。
Embodiment 13:
(1) 3.2084g ethylene glycol and 4.1463g citric acid are mixed and is dissolved in deionized water, is stirred under room temperature
The first solution is obtained, wherein the concentration of ethylene glycol and citric acid is respectively 0.064g/mL；0.0829g/mL, by sodium acetate, acetic acid
Manganese and ferric nitrate are separately added into the first solution, stir to get wet colloidal sol, and wherein sodium acetate, manganese acetate and ferric nitrate are molten first
Molar concentration in liquid is respectively 0.134mol/L, 0.1mol/L, 0.1mol/L；
(2) wet gel that step (1) obtains successively is subjected to aging, drying, pre-sintering and high temperature sintering, wherein aging temperature
Degree is 80 DEG C, and the time is 5 hours；Drying temperature is 150 DEG C, and the time is 24 hours；Pre-sintering temperature is 500 DEG C, pre-burning
The knot time is 5 hours；High temperature sintering temperature is 900 DEG C, and the time is 12 hours；It is cooled down rapidly under conditions of anhydrous and oxygen-free
Obtain sodium-ion battery positive material Na0.67Mn0.5Fe0.5O2；
(3) lithium acetate and tetraethyl orthosilicate are mixed, obtains mixture, the molar ratio of lithium salts and esters in mixture
In ethanol by mixture dissolution the second solution is obtained, so that lithium acetate molar concentration in the second solution is for 2:1
0.011mol/L；The sodium-ion battery positive material that step (2) obtains is added in the second solution, wherein sodium ion in liquor
Cell positive material concentration is 25g/L, obtains third solution.Obtained third solution is stirred into 5 hours at normal temperature, then
The drying of 80 DEG C of baking ovens, time are 10 hours, obtain solid-oxide, solid-oxide are pulverized last sintering, with 5 DEG C
Heating rate per minute is raised to 600 DEG C of 10 hours of heat preservation, is placed under conditions of anhydrous and oxygen-free and cools down rapidly, obtain lithium from
Sodium-ion battery positive material (the Li of sub- conductor cladding2SiO3@Na0.67Mn0.5Fe0.5O2)。
Embodiment 14:
(1) 3.2084g ethylene glycol and 4.1463g citric acid are mixed and is dissolved in deionized water, is stirred under room temperature
The first solution is obtained, wherein the concentration of ethylene glycol and citric acid is respectively 0.064g/mL；0.0829g/mL, by sodium acetate, acetic acid
Manganese and ferric nitrate are separately added into the first solution, stir to get wet colloidal sol, and wherein sodium acetate, manganese acetate and ferric nitrate are molten first
Molar concentration in liquid is respectively 0.134mol/L, 0.15mol/L, 0.05mol/L；
(2) wet gel that step (1) obtains successively is subjected to aging, drying, pre-sintering and high temperature sintering, wherein aging temperature
Degree is 80 DEG C, and the time is 5 hours；Drying temperature is 150 DEG C, and the time is 24 hours；Pre-sintering temperature is 500 DEG C, pre-burning
The knot time is 5 hours；High temperature sintering temperature is 900 DEG C, and the time is 12 hours；It is cooled down rapidly under conditions of anhydrous and oxygen-free
Obtain sodium-ion battery positive material Na0.67Mn0.75Fe0.25O2；
(3) lithium acetate and tetraethyl orthosilicate are mixed, obtains mixture, the molar ratio of lithium salts and esters in mixture
In ethanol by mixture dissolution the second solution is obtained, so that lithium acetate molar concentration in the second solution is for 2:1
0.011mol/L；The sodium-ion battery positive material that step (2) obtains is added in the second solution, wherein sodium ion in liquor
Cell positive material concentration is 25g/L, obtains third solution.Obtained third solution is stirred into 5 hours at normal temperature, then
The drying of 80 DEG C of baking ovens, time are 10 hours, obtain solid-oxide, solid-oxide are pulverized last sintering, with 2 DEG C
Heating rate per minute is raised to 600 DEG C of 5 hours of heat preservation, is placed under conditions of anhydrous and oxygen-free and cools down rapidly, obtains lithium ion
Sodium-ion battery positive material (the Li of conductor cladding2SiO3@Na0.67Mn0.75Fe0.25O2)。
Embodiment 15:
(1) 3.2084g ethylene glycol and 4.1463g citric acid are mixed and is dissolved in deionized water, is stirred under room temperature
The first solution is obtained, wherein the concentration of ethylene glycol and citric acid is respectively 0.064g/mL；0.0829g/mL, by sodium acetate, acetic acid
Manganese and ferric nitrate are separately added into the first solution, stir to get wet colloidal sol, and wherein sodium acetate, manganese acetate and ferric nitrate are molten first
Molar concentration in liquid is respectively 0.134mol/L, 0.16mol/L, 0.04mol/L；
(2) wet gel that step (1) obtains successively is subjected to aging, drying, pre-sintering and high temperature sintering, wherein aging temperature
Degree is 80 DEG C, and the time is 5 hours；Drying temperature is 150 DEG C, and the time is 24 hours；Pre-sintering temperature is 500 DEG C, pre-burning
The knot time is 5 hours；High temperature sintering temperature is 900 DEG C, and the time is 12 hours；It is cooled down rapidly under conditions of anhydrous and oxygen-free
Obtain sodium-ion battery positive material Na0.67Mn0.8Fe0.2O2；
(3) lithium acetate and tetraethyl orthosilicate are mixed, obtains mixture, the molar ratio of lithium salts and esters in mixture
In ethanol by mixture dissolution the second solution is obtained, so that lithium acetate molar concentration in the second solution is for 2:1
0.011mol/L；The sodium-ion battery positive material that step (2) obtains is added in the second solution, wherein sodium ion in liquor
Cell positive material concentration is 25g/L, obtains third solution.Obtained third solution is stirred into 5 hours at normal temperature, then
The drying of 80 DEG C of baking ovens, time are 10 hours, obtain solid-oxide, solid-oxide are pulverized last sintering, with 2 DEG C
Heating rate per minute is raised to 600 DEG C of 5 hours of heat preservation, is placed under conditions of anhydrous and oxygen-free and cools down rapidly, obtains lithium ion
Sodium-ion battery positive material (the Li of conductor cladding2SiO3@Na0.67Mn0.8Fe0.2O2)。
Application example:
(1) by the sodium-ion battery positive material for the lithium ion conductor cladding that in aforementioned present invention method prepared by embodiment 1
It is assembled into battery；
(2) battery performance is tested under the discharge current density of 0.1C (1C=200mAh/g), charge and discharge cycles
50 circles, compare with uncoated sodium-ion battery positive material, and battery discharge specific capacity as shown in Figure 3 significantly improves；
(3) to electricity under 0.05C, 0.1C, 0.2C, 0.5C, 1C, 2C and 5C (1C=200mAh/g) discharge current density
Pond high rate performance is tested, as a result as shown in figure 4, sodium-ion battery positive material (the Li of lithium ion conductor cladding2SiO3@
Na0.67Mn0.5Fe0.5O2) high rate performance is substantially better than uncoated sodium-ion battery positive material (Na0.67Mn0.5Fe0.5O2)。
Claims (2)
1. a kind of preparation method of lithium ion conductor coating modification sodium-ion battery positive material, it is characterised in that this method includes
Following steps:
(1) 3-5g ethylene glycol and 4-5g citric acid are mixed and is dissolved in deionized water, be stirred to obtain first under room temperature molten
Liquid, wherein the concentration of ethylene glycol and citric acid is respectively 0.06-0.1g/mL；0.08-0.1g/mL, by sodium acetate, manganese acetate and
Ferric nitrate is separately added into the first solution, stirs to get wet colloidal sol, and wherein sodium acetate, manganese acetate and ferric nitrate are in the first solution
Molar concentration be respectively 0.134mol/L, 0.1-0.16mol/L, 0.04-0.1mol/L；
(2) wet gel that step (1) obtains successively is subjected to aging, drying, pre-sintering and high temperature sintering, wherein aging temperature is
80-100 DEG C, the time is 5-10 hour；Drying temperature is 120-150 DEG C, and the time is 18-24 hour；Pre-sintering temperature is
500 DEG C, the pre-sintering time is 5 hours；High temperature sintering temperature is 800 DEG C -1000 DEG C, and the time is 12 hours；Finally in nothing
It is cooled down rapidly under conditions of water anaerobic, obtains sodium-ion battery positive material Na0.67MnxFe1-xO2, wherein 0.5≤x≤0.8；
(3) lithium acetate and Ester are mixed, obtains mixture, the molar ratio of lithium salts and esters is 2:1 in mixture, will
The mixture dissolves in ethanol, obtains the second solution, so that lithium acetate molar concentration in the second solution is 0.011-
0.22mol/L；The sodium-ion battery positive material that step (2) obtains is added in the second solution, so that sodium ion in liquor
Cell positive material concentration is 25g/L, obtains third solution, obtained third solution is stirred 5-10 hour at normal temperature,
Then 80 DEG C of -100 DEG C of baking ovens drying, drying time are 10-12 hour, obtain solid-oxide, solid-oxide is ground
At being sintered after powder, with 2 DEG C -5 DEG C heating rates per minute, 500 DEG C of 5-10 hours of -600 DEG C of heat preservations are raised to, finally
It is cooled down rapidly under conditions of anhydrous and oxygen-free, obtains the sodium-ion battery positive material of lithium ion conductor cladding.
2. preparation method as described in claim 1, which is characterized in that the Ester in the step (3) is positive silicic acid
Tetra-ethyl ester, butyl titanate, tetrabutyl zirconate or tetrabutyltin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811223499.7A CN109449395A (en) | 2018-10-19 | 2018-10-19 | A kind of preparation method of lithium ion conductor coating modification sodium-ion battery positive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811223499.7A CN109449395A (en) | 2018-10-19 | 2018-10-19 | A kind of preparation method of lithium ion conductor coating modification sodium-ion battery positive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109449395A true CN109449395A (en) | 2019-03-08 |
Family
ID=65546788
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811223499.7A Pending CN109449395A (en) | 2018-10-19 | 2018-10-19 | A kind of preparation method of lithium ion conductor coating modification sodium-ion battery positive material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109449395A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110034333A (en) * | 2019-04-16 | 2019-07-19 | 山东海容电源材料股份有限公司 | A kind of high temperature resistant nonaqueous electrolytic solution |
| WO2023092930A1 (en) * | 2021-11-29 | 2023-06-01 | 横店集团东磁股份有限公司 | Sodium ion positive electrode material and preparation method therefor, and sodium ion battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413930A (en) * | 2013-07-30 | 2013-11-27 | 南京航空航天大学 | Modified LiNi1/2Mn3/2O4 cathode material prepared by coating with lithium ion conductor Li2MO3 (M=Ti, Si or Zr) and preparation method thereof |
| CN104022276A (en) * | 2014-06-09 | 2014-09-03 | 南京航空航天大学 | Clad modified layered cathode material of lithium-ion battery and preparation method of layered cathode material |
| US20150311507A1 (en) * | 2012-06-29 | 2015-10-29 | Toyota Jidosha Kabushiki Kaisha | Composite active material, solid state battery and method for producing composite active material |
-
2018
- 2018-10-19 CN CN201811223499.7A patent/CN109449395A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150311507A1 (en) * | 2012-06-29 | 2015-10-29 | Toyota Jidosha Kabushiki Kaisha | Composite active material, solid state battery and method for producing composite active material |
| CN103413930A (en) * | 2013-07-30 | 2013-11-27 | 南京航空航天大学 | Modified LiNi1/2Mn3/2O4 cathode material prepared by coating with lithium ion conductor Li2MO3 (M=Ti, Si or Zr) and preparation method thereof |
| CN104022276A (en) * | 2014-06-09 | 2014-09-03 | 南京航空航天大学 | Clad modified layered cathode material of lithium-ion battery and preparation method of layered cathode material |
Non-Patent Citations (2)
| Title |
|---|
| JIANGFENG NI等: "Improved electro chemical performance of layered LiNi0.4Co0.2Mn0.4O2 via Li2ZrO3 coating", 《ELECTROCHIMICA ACTA》 * |
| WANG HUIBO等: "Different Effects of Al Substitution for Mn or Fe on the Structure and Electrochemical Properties of Na0.67Mn0.5Fe0.5O2 as a Sodium Ion Battery Cathode Material", 《INORGANIC CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110034333A (en) * | 2019-04-16 | 2019-07-19 | 山东海容电源材料股份有限公司 | A kind of high temperature resistant nonaqueous electrolytic solution |
| WO2023092930A1 (en) * | 2021-11-29 | 2023-06-01 | 横店集团东磁股份有限公司 | Sodium ion positive electrode material and preparation method therefor, and sodium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109879331A (en) | The nickelic tertiary cathode material and preparation method of a kind of fast-ionic conductor cladding and its lithium ion battery being prepared | |
| CN103474625B (en) | A kind of Olivine-type Cathode Material in Li-ion Batteries method for coating of nucleocapsid structure | |
| CN103928672B (en) | A kind of positive electrode active material for lithium ion battery and preparation method thereof | |
| CN105304885B (en) | A kind of aluminum secondary battery vanadium oxide positive electrode materials and preparation method thereof | |
| CN102412390A (en) | Preparation method of Li4Ti5O12 wrapped natural graphite for lithium ion battery cathode | |
| CN107978739A (en) | A kind of fluorinated phosphate manganese titanium sodium/carbon composite and preparation method thereof and the application as sodium ion positive electrode | |
| CN103219507B (en) | Composite material with tubular structure as well as preparation method and application thereof | |
| CN108336315A (en) | A kind of preparation method of the lithium ion battery nickel lithium manganate cathode material of coating modification | |
| CN103474644B (en) | There is lithium titanate composite electrode material and the preparation method of fluoride surface coating layer | |
| CN104852028A (en) | Lithium titanate/graphene composite cathode material for lithium ion battery | |
| CN105098158B (en) | A kind of lithium-enriched cathodic material of lithium ion battery of zirconium doping and preparation method thereof | |
| CN103390748B (en) | A kind of preparation method of alumina-coated lithium cobaltate cathode material | |
| CN107369815A (en) | A kind of lithium rechargeable battery composite positive pole and preparation method thereof | |
| CN113666420B (en) | Bimetal niobium oxide and carbon composite material thereof, preparation method and application | |
| CN104051725A (en) | Preparation method for high-voltage nickel-cobalt-manganese-lithium oxide positive electrode material | |
| CN105355923A (en) | Surface coated lithium ion battery cathode material, and preparation method thereof | |
| CN103872313B (en) | Anode material for lithium-ion batteries LiMn2‑2xM(II)xSixO4And preparation method thereof | |
| CN101704681A (en) | Method for preparing lithium titanate with spinel structure | |
| CN107946564A (en) | Rich sodium manganese base Na4Mn2O5/Na0.7MnO2Composite material and its preparation method and application | |
| CN109449395A (en) | A kind of preparation method of lithium ion conductor coating modification sodium-ion battery positive material | |
| CN109904438A (en) | A kind of magnesium barium oxide and its preparation method and application | |
| CN103456945A (en) | Preparation method of low-cost lithium ion battery anode material | |
| CN104425799B (en) | A kind of iron borate lithium block type electrode and preparation method thereof | |
| CN110563052B (en) | Preparation method of carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material | |
| CN107871860A (en) | Preparation method using metatitanic acid lithium cladding manganese cobalt oxide and products thereof and application |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190308 |
|
| WD01 | Invention patent application deemed withdrawn after publication |