CN106340627B - A kind of preparation method of sodium-ion battery positive material - Google Patents
A kind of preparation method of sodium-ion battery positive material Download PDFInfo
- Publication number
- CN106340627B CN106340627B CN201610890064.2A CN201610890064A CN106340627B CN 106340627 B CN106340627 B CN 106340627B CN 201610890064 A CN201610890064 A CN 201610890064A CN 106340627 B CN106340627 B CN 106340627B
- Authority
- CN
- China
- Prior art keywords
- sodium
- source
- manganese
- preparation
- oxidant
- 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.)
- Active
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
- H01M4/48—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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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 discloses a kind of preparation method of sodium-ion battery positive material, comprising: by sodium source, source of iron and manganese source, is uniformly mixed, obtains mixture；The mixture is mixed with oxidant, oxidation reaction is carried out by ultrasonic vibration, obtains reactant；Presoma will be obtained after reactant drying, activation；The presoma is calcined in air, is quickly cooled down up to the positive electrode；Wherein the positive electrode is hexagonal structure sodium ion compound N a2/3Fe1/2Mn1/2O2.The present invention uses the higher source of iron of activity and manganese source for raw material, and improves the activity of reactant using oxidant pre-oxidation, to reduce the synthesis temperature of material, shortens generated time, the crystallinity of products therefrom is high and has excellent chemical property.
Description
Technical field
The present invention relates to a kind of sodium-ion battery field more particularly to a kind of preparation sides of sodium-ion battery positive material
Method.
Background technique
In recent years, due to the rapid exhaustion of lithium resource, people just actively find alternative battery system.Sodium-ion battery
Since sodium element reserves abundant and cheap price receive significant attention.Na2/3Fe1/2Mn1/2O2It is a kind of novel sodium ion
Cell positive material, it has hexagonal structure (P2) and octahedron crystal form (O3) two kinds of crystal structures, wherein hexagonal structure
Na2/3Fe1/2Mn1/2O2Theoretical specific capacity is up to 260mAh/g, is suitable as the positive electrode of energy-storage battery；However, lower electricity
Electron conductivity and ionic conductivity inhibit and the performance of chemical property (such as capacity, cycle performance, high rate performance).
Hexagonal structure Na is prepared at present2/3Fe1/2Mn1/2O2Method have high temperature solid-state method, coprecipitation and method of electrostatic spinning
Deng.Although common high temperature solid-state method process is simple, raw material need to mix for a long time and be difficult to be uniformly mixed, due to calcination temperature
Height, so that product grain is coarse and particle diameter distribution is uneven, properties of product are poor.Coprecipitation process process is complex, and easily
Impurity is introduced in the product, and product particle size is larger, and capacity is lower.Although method of electrostatic spinning can prepare linear nanoscale
Product, but equipment and environment (humidity) are required very high, high molecular polymer need to additionally be added as binder, it is at high cost,
Yield is small, and product tap density is low, and chemical property is poor.
It is above-mentioned reported to prepare hexagonal structure Na2/3Fe1/2Mn1/2O2Method in, mostly with inorganic source of iron and inorganic manganese source
For raw material, synthesis temperature height (general 900 DEG C~1000 DEG C), time are long.In addition, the Na that the above method is prepared2/3Fe1/2Mn1/ 2O2Though positive electrode belongs to hexagonal crystal system, product grain is irregular pattern, does not show apparent hexagonal structure
Particle shape looks illustrate that product crystallinity is not high, this will largely influence the chemical property of material.
Summary of the invention
In order to solve the above technical problems, the technical scheme is that using a kind of sodium-ion battery positive material preparation
Method, comprising:
By sodium source, source of iron and manganese source, it is uniformly mixed, obtains mixture；
The mixture is mixed with oxidant, oxidation reaction is carried out by ultrasonic vibration, obtains reactant；
Presoma will be obtained after reactant drying, activation；
The presoma is calcined in air, is quickly cooled down up to the positive electrode；
Wherein the positive electrode is hexagonal structure sodium ion compound N a2/3Fe1/2Mn1/2O2。
Preferably, the sodium source is selected from sodium oxide molybdena, sodium carbonate, sodium nitrate, sodium hydroxide, sodium acetylide, heparin sodium, triazole
One or more of sodium, Sodamide, sodium methoxide, sodium ethoxide, sodium phenate.
Preferably, the source of iron is selected from ironic citrate, ferrous oxalate, ferrous gluconate, LI agar, phthalocyanine
One or more of iron, ferrocene.
Preferably, the manganese source is manganese acetate, manganese naphthenate, manganese stearate, Mn-Gly, ten hydroxyls, two manganese, levulinic
One or more of ketone manganese.
Preferably, the sodium source, source of iron and manganese source are (3.9~4.1) by the molar ratio of tri- kinds of elements of Na, Fe, Mn: (2.9
~3.1): (2.9~3.1).
Preferably, described mix the mixture with oxidant is specially by the oxidant and the mixture by oxygen
The molar ratio mixing of the sum of agent and Fe+Mn element, the molar ratio are 1:(1~10).
Preferably, the oxidant is selected from hydrogen peroxide, nitric acid, the concentrated sulfuric acid, permonosulphuric acid, peroxy-disulfuric acid, ammonium persulfate
One or more of.
Preferably, the frequency of the ultrasonic oscillation are as follows: 20~128kHz.
Preferably, the drying, activation specifically:
The reactant is dried at 50 DEG C~100 DEG C；
Mechanical activation 0.5h~12h is carried out after drying, the revolving speed of the mechanical activation is 100~500r/min.
Preferably, the presoma is calcined in air specifically:
By the presoma at 650~900 DEG C in air calcining 1~for 24 hours.
The present invention provides a kind of preparation method of sodium-ion battery, in particular to a kind of to prepare hexagonal structure Na2/3Fe1/ 2Mn1/2O2Method.It uses source of iron and manganese source for raw material, first raw material is aoxidized with hydrogen peroxide, while utilizing ultrasonic vibration
Enhanced oxidation process, by after oxidation mixture mechanical activation, calcining, be quickly cooled down up to well-crystallized and have template
Na2/3Fe1/2Mn1/2O2Positive electrode.Since the valence state of Fe, Mn in required product are compared with the height in raw material, so in preparation process
In need to aoxidize it, and general mechanical activation method is using strong oxidizer sodium peroxide as raw material, but this original
There is great security risk in material, be also passed through oxygen in calcination process or compressed air is aoxidized in use,
In addition there are extend calcination time to achieve the effect that oxidation.And the present invention carries out pre- oxygen to raw material using cheap hydrogen peroxide
Change, and strengthen this effect with sonic oscillation, has pre-oxidized Fe, Mn element in raw material just before being calcined
Certain valence state shortens calcination time to reduce calcination temperature, has saved cost.
In addition, sonic oscillation enhances oxidation process since the oxidation of hydrogen peroxide improves the activity of material, from
And calcination temperature is reduced, shorten calcination time.Products obtained therefrom crystallinity is high, has excellent chemical property.
In conclusion the preparation method of sodium ion positive electrode provided by the invention has the beneficial effect that (1) due to organic
That there are decomposition temperatures is low for metal salt itself, and the high characteristic of decomposition product activity, greatly reducing calcination temperature, (minimum 650 DEG C i.e.
Can synthesize), shorten calcination time (minimum 1h can be synthesized).
(2) it uses hydrogen peroxide to carry out pre-oxidation treatment to raw material as oxidant, the activity and knot of reactant can be improved
Brilliant ability shortens calcination time to reduce calcination temperature, can synthesize the product of well-crystallized.And hydrogen peroxide
Foaming effect can be effectively prevented the generation of the agglomeration of product in calcination process again.Sonic oscillation can not only promote
The progress of oxidation reaction, enhanced oxidation effect, and can also sufficiently ensure the uniformity of raw material mixing, to obtain uniform component
Product.
(3) Na of this method preparation2/3Fe1/2Mn1/2O2With intact hexagonal crystal structures and pattern, crystallinity is high, because
This material structure is stablized, charge/discharge capacity with higher, excellent high rate performance and cycle performance.
Detailed description of the invention
Na is prepared in Fig. 1 embodiment 12/3Fe1/2Mn1/2O2Scanning electron microscope (SEM) photograph；
Na is prepared in Fig. 2 embodiment 22/3Fe1/2Mn1/2O2Scanning electron microscope (SEM) photograph；
Na is prepared in Fig. 3 comparative example 12/3Fe1/2Mn1/2O2Scanning electron microscope (SEM) photograph；
Na is prepared in Fig. 4 comparative example 22/3Fe1/2Mn1/2O2Scanning electron microscope (SEM) photograph；
Na is prepared in Fig. 5 comparative example 32/3Fe1/2Mn1/2O2Scanning electron microscope (SEM) photograph；
Na in Fig. 6 embodiment 12/3Fe1/2Mn1/2O2First charge-discharge curve；
Na in Fig. 7 comparative example 32/3Fe1/2Mn1/2O2First charge-discharge curve.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, With reference to embodiment
The present invention is described in further detail.
The present invention provides a kind of preparation methods of sodium-ion battery, in particular to a kind of to prepare hexagonal structure Na2/3Fe1/ 2Mn1/2O2Method.Include:
By sodium source, source of iron and manganese source, it is uniformly mixed, obtains mixture；
The mixture is mixed with oxidant, oxidation reaction is carried out by ultrasonic vibration, obtains reactant；
Presoma will be obtained after reactant drying, activation；
The presoma is calcined in air, is quickly cooled down up to the positive electrode；
Wherein the positive electrode is hexagonal structure sodium ion compound N a2/3Fe1/2Mn1/2O2。
According to the present invention, the chemical formula of the sodium ion compound preferably prepared is Na2/3Fe1/2Mn1/2O2.It ties in order to obtain
Brilliant degree is high, the uniform product of structure, is organic salt present invention preferably uses source of iron and manganese source, is selected from according to sodium source of the present invention
Sodium oxide molybdena, sodium carbonate, sodium nitrate, sodium hydroxide, sodium acetylide, heparin sodium, 1-Sodium-1,2,4-Triazole, Sodamide, sodium methoxide, sodium ethoxide, phenol
One or more of sodium, the source of iron are selected from ironic citrate, ferrous oxalate, ferrous gluconate, LI agar, phthalocyanine
One or more of iron, ferrocene, the manganese source are manganese acetate, manganese naphthenate, manganese stearate, Mn-Gly, ten hydroxyls two
One or more of manganese, manganese acetylacetonate.
In order to further control reaction, the sodium source, source of iron and manganese source are by the molar ratio of tri- kinds of elements of Na, Fe, Mn
(3.9~4.1): (2.9~3.1): (2.9~3.1).
After mixture is prepared, the mixture is mixed with oxidant, specially mixes the oxidant with described
Object is closed by the molar ratio mixing of the sum of oxidant and Fe+Mn element, the molar ratio is 1:(1~10).The oxidant is selected from
One or more of hydrogen peroxide, nitric acid, the concentrated sulfuric acid, permonosulphuric acid, peroxy-disulfuric acid, ammonium persulfate.More preferably peroxidating
One or more of hydrogen, the concentrated sulfuric acid, permonosulphuric acid, ammonium persulfate, most preferably hydrogen peroxide.
It needs to carry out ultrasonic oscillation in oxidation reaction, it is proposed, according to the invention, the frequency of the ultrasonic oscillation are as follows: 20~
128kHz.After obtaining reactant, to reactant drying, the drying, activation are activated specifically: by the reactant 50
DEG C~100 DEG C at dry；Mechanical activation 0.5h~12h is carried out after drying, the revolving speed of the mechanical activation is 100~500r/
min。
Presoma after drying and activation is sintered, and dispels the moisture in the presoma, and make forerunner at high temperature
It is combined between each element in body, forms crystallization, the presoma is calcined in air specifically: by the presoma
At 650~900 DEG C in air calcining 1~for 24 hours.
The following are the specific embodiment of the invention.
Embodiment 1
Na:Fe:Mn=4.05:3:3 weighs sodium ethoxide, ferrous oxalate and manganese acetate in molar ratio, is uniformly mixed, and then adds
Enter the hydrogen peroxide (in molar ratio hydrogen peroxide: (Fe+Mn)=3:1) that concentration is 20%, 90 minutes (frequencies of oscillation of sonic oscillation
For 80kHz), gained mixture is dried at 80 DEG C, then mechanical activation 4 hours (revolving speed 300r/min) obtains precursor
End calcines presoma 8 hours at 800 DEG C in air, and calcined powder is immediately placed in liquid nitrogen and is quickly cooled down i.e.
Obtain the Na of hexagonal structure2/3Fe1/2Mn1/2O2.As shown in Figure 1, to prepare Na in embodiment 12/3Fe1/2Mn1/2O2Scanning electron microscope
Scheme, can be seen that the structure of hexagonal structure is uniform in figure, crystallinity is high.
Embodiment 2
Na:Fe:Mn=4:3:3.05 weighs sodium hydroxide, ironic citrate and Mn-Gly in molar ratio, is uniformly mixed, with
The hydrogen peroxide (in molar ratio hydrogen peroxide: (Fe+Mn)=10:1) that concentration is 5%, sonic oscillation (vibration in 160 minutes are added afterwards
Swinging frequency is 20kHz), gained mixture is dried at 70 DEG C, then carries out 12 hours (revolving speed 200r/ of mechanical activation
Min precursor powder) is obtained, presoma is calcined 1 hour in air at 900 DEG C, calcined powder is immediately placed on sky
The Na up to hexagonal structure is quickly cooled down in gas2/3Fe1/2Mn1/2O2.As shown in Fig. 2, to prepare Na in embodiment 22/3Fe1/ 2Mn1/2O2Scanning electron microscope (SEM) photograph, can be seen that the structure of hexagonal structure is uniform in figure, crystallinity is high.
Embodiment 3
Na:Fe:Mn=4:2.95:2.9 weighs Sodamide, ferrous gluconate and manganese stearate in molar ratio, and mixing is equal
It is even, then it is added the hydrogen peroxide (in molar ratio hydrogen peroxide: (Fe+Mn)=1:1) that concentration is 50%, sonic oscillation 10 minutes
(frequency of oscillation 128kHz) dries gained mixture at 50 DEG C, and then carrying out mechanical activation 0.5 hour, (revolving speed is
500r/min), gained mixture is calcined 24 hours in air at 650 DEG C, after calcined powder is wrapped up with copper foil
It is immediately placed on the Na being quickly cooled down in water up to hexagonal structure2/3Fe1/2Mn1/2O2。
Embodiment 4
Na:Fe:Mn=4.1:3.05:3 weighs sodium carbonate, ironic citrate and Mn-Gly in molar ratio, is uniformly mixed, with
Nitric acid (in molar ratio nitric acid: (Fe+Mn)=5:1) sonic oscillation 240 minutes that concentration is 70% is added afterwards, and (frequency of oscillation is
60kHz), gained mixture is dried at 100 DEG C, then mechanical activation 15 hours (revolving speed 100r/min) is carried out, by institute
It obtains mixture to calcine 16 hours in air at 750 DEG C, calcined powder is immediately placed in air and is quickly cooled down to obtain the final product
The Na of hexagonal structure2/3Fe1/2Mn1/2O2。
Embodiment 5
It is equal to weigh sodium acetylide, ironic citrate hydration and manganese acetate, mixing by Na:Fe:Mn=3.96:2.9:3.1 in molar ratio
It is even, nitric acid (in molar ratio nitric acid: (Fe+Mn)=6:1) 240 minutes (oscillation frequencies of sonic oscillation that concentration is 10% are then added
Rate is 60kHz), gained mixture is dried at 90 DEG C, then carries out mechanical activation 15 hours (revolving speed 100r/min), it will
Gained mixture is calcined 16 hours in air at 750 DEG C, and calcined powder is immediately placed in air and is quickly cooled down i.e.
Obtain the Na of hexagonal structure2/3Fe1/2Mn1/2O2。
Embodiment 6
Na:Fe:Mn=3.9:3.1:2.95 weighs sodium nitrate, ferrous oxalate and manganese stearate in molar ratio, is uniformly mixed,
Then it is added the sulfuric acid (in molar ratio sulfuric acid: (Fe+Mn)=3:1) that concentration is 90%, (frequency of oscillation is for sonic oscillation 90 minutes
80kHz), gained mixture is dried at 85 DEG C, then mechanical activation 4 hours (revolving speed 300r/min) obtains precursor
End calcines presoma 8 hours at 800 DEG C in air, and calcined powder is immediately placed in liquid nitrogen and is quickly cooled down i.e.
Obtain the Na of hexagonal structure2/3Fe1/2Mn1/2O2
Comparative example 1
Na:Fe:Mn=4.05:3:3 weighs sodium peroxide, di-iron trioxide, manganese dioxide in molar ratio, is uniformly mixed,
The hydrogen peroxide (in molar ratio hydrogen peroxide: (Fe+Mn)=3:1) that concentration is 20%, sonic oscillation (vibration in 90 minutes is then added
Swinging frequency is 80kHz), gained mixture is dried at 80 DEG C, before then mechanical activation 4 hours (revolving speed 300r/min) obtains
Body powder is driven, presoma is calcined 8 hours in air at 800 DEG C, calcined powder is immediately placed in liquid nitrogen quickly
The cooling Na up to hexagonal structure2/3Fe1/2Mn1/2O2.It is illustrated in figure 3 in comparative example 1 and prepares Na2/3Fe1/2Mn1/2O2Scanning
Electron microscope, it can be seen from the figure that the structure is uneven, not of uniform size, crystallinity is lower.
Comparative example 2
Na:Fe:Mn=4.05:3:3 weighs sodium ethoxide, ferrous oxalate and manganese acetate in molar ratio, is uniformly mixed, then machine
Tool activates 4 hours (revolving speed 300r/min) to obtain precursor powder, and presoma is calcined 8 hours in air at 800 DEG C, will
Calcined powder is immediately placed on the Na being quickly cooled down in liquid nitrogen up to hexagonal structure2/3Fe1/2Mn1/2O2.It is illustrated in figure 4 pair
Na is prepared in ratio 12/3Fe1/2Mn1/2O2Scanning electron microscope (SEM) photograph, it is not of uniform size it can be seen from the figure that the structure is uneven,
Crystallinity is lower.
Comparative example 3
Na:Fe:Mn=4.05:3:3 weighs sodium peroxide, di-iron trioxide, manganese dioxide in molar ratio, is uniformly mixed,
Then mechanical activation 4 hours (revolving speed 300r/min) obtains precursor powder, and presoma is calcined 8 at 800 DEG C in air
Hour, calcined powder is immediately placed on to the Na being quickly cooled down in liquid nitrogen up to hexagonal structure2/3Fe1/2Mn1/2O2.Such as Fig. 5 institute
It is shown as preparing Na in comparative example 12/3Fe1/2Mn1/2O2Scanning electron microscope (SEM) photograph, it can be seen from the figure that the structure is uneven, greatly
Small different, crystallinity is lower.
The preparation of battery
Using the material of Examples 1 to 6 preparation as positive electrode active materials, it (is gathered inclined two with acetylene black (conductive agent), PVDF
Vinyl fluoride, bonding agent) weighed according to the mass ratio of 80:10:10 after, in mortar grind a period of time, be allowed to uniformly mixed, add
Enter N-Methyl pyrrolidone (NMP), incessantly grinding a period of time, finally obtains uniform dark thick slurry like material.?
The uniform sizing material obtained after grinding is placed on aluminium foil, is coated into film in homogeneous thickness.It is to electrode, glass with metallic sodium piece
Glass tunica fibrosa is diaphragm, the NaClO of 1mol/L4/ PC (propene carbonate) is electrolyte, in the argon atmosphere gloves of anhydrous and oxygen-free
CR2032 type button cell is assembled into case.Charge-discharge test, gained test knot will be carried out after battery standing 24 hours installed
Fruit such as table 1.
The chemical property comparison of sample is prepared in each implementation column of table 1
Remarks: with metal Na for electrode, charging/discharging voltage range 1.5-4.2V, 25 DEG C of constant temperature when test.
By the data and Fig. 6 of table 1 and the comparison of Fig. 7 as can be seen that the reality of preparation method provided by the invention preparation
The sodium ion electricity of the formation of positive electrode prepared by the sodium-ion battery and comparative example 1~3 for applying the positive electrode preparation of example 1~6
Pond is compared, and initial charge specific capacity is above comparative example, and capacity retention ratio is above comparative example.
The above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
Limitation of the invention, protection scope of the present invention should be defined by the scope defined by the claims..For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change
It also should be regarded as the scope of protection of the patent of the present invention into retouching.
Claims (7)
1. a kind of preparation method of sodium-ion battery positive material characterized by comprising
By sodium source, source of iron and manganese source, it is uniformly mixed, obtains mixture；
The mixture is mixed with oxidant, oxidation reaction is carried out by ultrasonic vibration, obtains reactant；
Presoma will be obtained after reactant drying, activation；
The presoma is calcined in air, is quickly cooled down up to the positive electrode；
Wherein the positive electrode is hexagonal structure sodium ion compound N a2/3Fe1/2Mn1/2O2；
The source of iron is in ironic citrate, ferrous oxalate, ferrous gluconate, LI agar, FePC, ferrocene
It is one or more of；The manganese source is manganese acetate, manganese naphthenate, manganese stearate, Mn-Gly, ten hydroxyls, two manganese, manganese acetylacetonate
One or more of；The oxidant is hydrogen peroxide.
2. preparation method according to claim 1, which is characterized in that the sodium source is selected from sodium oxide molybdena, sodium carbonate, nitric acid
One or more of sodium, sodium hydroxide, sodium acetylide, heparin sodium, 1-Sodium-1,2,4-Triazole, Sodamide, sodium methoxide, sodium ethoxide, sodium phenate.
3. preparation method according to claim 1, which is characterized in that the sodium source, source of iron and manganese source press Na, Fe, Mn tri-
The molar ratio of kind element is (3.9 ~ 4.1): (2.9 ~ 3.1): (2.9 ~ 3.1).
4. preparation method according to claim 1, which is characterized in that described to mix the mixture specifically with oxidant
To mix the oxidant by the molar ratio of the sum of oxidant and Fe+Mn element with the mixture, the molar ratio is 1:
(1 ~ 10).
5. preparation method according to claim 1, which is characterized in that the frequency of the ultrasonic oscillation are as follows:
20~128 kHz.
6. preparation method according to claim 1, which is characterized in that the drying, activation specifically:
The reactant is dried at 50 DEG C ~ 100 DEG C；
Mechanical activation 0.5h~12h is carried out after drying, the revolving speed of the mechanical activation is 100 ~ 500r/min.
7. preparation method according to claim 1, which is characterized in that calcine the presoma in air specific
Are as follows:
The presoma is calcined in air to 1~24 h at 650~900 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610890064.2A CN106340627B (en) | 2016-10-12 | 2016-10-12 | A kind of preparation method of sodium-ion battery positive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610890064.2A CN106340627B (en) | 2016-10-12 | 2016-10-12 | A kind of preparation method of sodium-ion battery positive material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106340627A CN106340627A (en) | 2017-01-18 |
| CN106340627B true CN106340627B (en) | 2019-05-17 |
Family
ID=57839859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610890064.2A Active CN106340627B (en) | 2016-10-12 | 2016-10-12 | A kind of preparation method of sodium-ion battery positive material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106340627B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108110236A (en) * | 2017-12-14 | 2018-06-01 | 东北大学 | A kind of sodium-ion battery positive material and preparation method thereof |
| CN108565429B (en) * | 2018-04-19 | 2020-05-19 | 齐鲁工业大学 | NaFeS as negative electrode material of sodium-ion battery2Preparation method of/C composite material |
| CN110970612B (en) * | 2018-09-29 | 2022-05-06 | 中国科学院大连化学物理研究所 | Preparation of transition metal oxide positive electrode material and application of transition metal oxide positive electrode material in sodium ion battery |
| CN110112375B (en) * | 2019-03-22 | 2021-07-30 | 南京大学 | Double-transition metal manganese-based layered positive electrode material of sodium ion battery |
| CN111180704A (en) * | 2020-01-07 | 2020-05-19 | 湖南工程学院 | Sodium-ion battery positive electrode material and preparation method and application thereof |
| CN114566650B (en) * | 2022-03-04 | 2024-02-23 | 中南大学 | Sodium-supplementing additive for positive electrode of sodium ion battery, sodium-supplementing method, positive electrode and flexible electrode |
| CN115148984B (en) * | 2022-09-02 | 2023-01-03 | 湖州超钠新能源科技有限公司 | O3-P2 composite phase sodium ion positive electrode material and preparation method and application thereof |
| CN115611323B (en) * | 2022-11-25 | 2023-03-21 | 江苏正力新能电池技术有限公司 | Positive electrode material, preparation method thereof, positive electrode piece and sodium-ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104953172A (en) * | 2015-07-24 | 2015-09-30 | 上海中聚佳华电池科技有限公司 | Sodium-ion battery cathode materials, preparation method of sodium-ion battery cathode materials, and sodium-ion batteries |
| JP2016110991A (en) * | 2014-11-27 | 2016-06-20 | 学校法人東京理科大学 | Positive electrode for sodium secondary battery and sodium secondary battery |
-
2016
- 2016-10-12 CN CN201610890064.2A patent/CN106340627B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016110991A (en) * | 2014-11-27 | 2016-06-20 | 学校法人東京理科大学 | Positive electrode for sodium secondary battery and sodium secondary battery |
| CN104953172A (en) * | 2015-07-24 | 2015-09-30 | 上海中聚佳华电池科技有限公司 | Sodium-ion battery cathode materials, preparation method of sodium-ion battery cathode materials, and sodium-ion batteries |
Non-Patent Citations (2)
| Title |
|---|
| Enhanced Sodium Ion Storage Behavior of P2-Type Na2/3Fe1/2Mn1/2O2 Synthesized via a Chelating Agent Assited Route;Ying Bai;《APPLIED MATERIALS & INTERFACES》;20160106;全文 * |
| Stable layered P3/P2 Na0.66Co0.5Mn0.5O2 cathode materials for sodium-ion batteries;Xiaoqing Chen;《Journal of Materials Chemistry A》;20151107;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106340627A (en) | 2017-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106340627B (en) | A kind of preparation method of sodium-ion battery positive material | |
| CN101693532B (en) | Method for preparing lithium ferrous phosphate | |
| CN1208241C (en) | Wet chemistry method for preparing lithium iron phosphate | |
| US11108037B2 (en) | Method for preparing graphene/ternary material composite for use in lithium ion batteries and product thereof | |
| JP4223463B2 (en) | Method for producing olivine type lithium iron phosphate cathode material | |
| CN102208610B (en) | Preparation method of carbon coated MnO cathode material | |
| CN105140492A (en) | Cobalt-nickel lithium manganate composite positive electrode material with surface wrapped by lithium zirconate and preparation method | |
| CN102315433A (en) | Graphene loaded Cu-CuxO composite material and preparation method thereof | |
| WO1998029915A1 (en) | Anode active material, its producing process, and lithium ion secondary cell using the anode active material | |
| CN102738458A (en) | Surface modification method of lithium-rich cathode material | |
| CN103359795A (en) | Cobalt-covered lithium ion cell anode material precursor as well as preparation method and application | |
| CN108933237B (en) | Preparation method and application of lithium ion battery positive electrode material | |
| CN103560246B (en) | A kind of preparation method of lithium ion battery anode material lithium iron phosphate | |
| CN102583583B (en) | A kind of lithium ion battery manganese cobalt lithium oxide anode material and preparation method thereof | |
| CN109167050A (en) | The production method of inexpensive 551530 type tertiary cathode material of high capacity | |
| CN104393272A (en) | Lithium titanate cathode composite material and preparation method | |
| CN103474645A (en) | Preparation method for lithium titanate | |
| CN102956884A (en) | Lithium-rich manganese-based material and preparation method thereof | |
| CN109775726B (en) | Preparation method of prussian blue material | |
| CN104795563A (en) | Method for manufacturing lithium ion batteries cathode material LiFeBO3/C by citric acid method | |
| CN108666555A (en) | A kind of multistage γ-Fe2O3The preparation method of/C nano piece negative material | |
| WO2014024924A1 (en) | Positive-electrode active material for lithium secondary battery, manufacturing method therefor, positive electrode for lithium secondary battery, and lithium secondary battery provided with said positive electrode | |
| CN111924864A (en) | MnO/MgO composite negative electrode material of lithium ion battery and preparation method thereof | |
| Liu et al. | Improving the electrochemical performance of single crystal LiNi0. 5Mn1. 5O4 cathode materials by Y–Ti doping and unannealing process | |
| CN108123105A (en) | A kind of manganese-base oxide positive electrode of electrode layer modification and preparation and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |