CN110289411A - A kind of fluorinated phosphate zirconium manganese sodium/carbon composite, positive electrode, anode and sodium-ion battery and preparation method thereof - Google Patents
A kind of fluorinated phosphate zirconium manganese sodium/carbon composite, positive electrode, anode and sodium-ion battery and preparation method thereof Download PDFInfo
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- CN110289411A CN110289411A CN201910590755.4A CN201910590755A CN110289411A CN 110289411 A CN110289411 A CN 110289411A CN 201910590755 A CN201910590755 A CN 201910590755A CN 110289411 A CN110289411 A CN 110289411A
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- 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
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- 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
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- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to sodium-ion battery Material Fields, specifically disclose a kind of fluorinated phosphate zirconium manganese sodium/carbon composite, are the in-situ composite of fluorinated phosphate zirconium manganese sodium, carbon, the chemical formula Na of the fluorinated phosphate zirconium manganese sodium3ZrMn(PO4)2F3.The present invention also provides the preparation method and application of the material.The present invention provides the in-situ composites of a kind of completely new chemical formula and crystal phase structure, and find that the composite material has the electric properties such as high charge-discharge specific capacity, good high rate performance and stable circulation performance in sodium-ion battery.
Description
Technical field
The present invention relates to a kind of sodium-ion battery Material Field, tool is related to the positive electrode active materials body of sodium-ion battery.
Background technique
Lithium ion battery is due to having occupied rapidly portable with advantages such as high-energy density, high stability, long-lives
Electronic product leads to lithium ion battery valence so that lithium ion battery lithium valence during a wide range of promote and apply is constantly soaring
Lattice are high.Therefore, application of the lithium ion battery in extensive storage field is difficult to really realize.Sodium-ion battery is due to sodium
Resource reserves are abundant, environmental-friendly, it is considered to be a kind of ideal extensive storage application technology and obtain the extensive of the world
Concern.
Though seeing the difference of only embedded ion on sodium-ion battery and lithium ion battery surface, it is under the jurisdiction of different necks
Domain, the requirement to electrode material are completely different.For example, sodium ion is bigger than lithium ion by 55% or so, sodium ion is in identical structure
Insertion in material and diffusion often all relative difficulty, while the structure change of material can be bigger after being embedded in, thus electrode material
Specific capacity, dynamic performance and cycle performance etc. be all correspondingly deteriorated.Compared to field of lithium ion battery, sodium-ion battery neck
There are also many technical problems needs to overcome in domain, and technical maturity seriously lags behind lithium ion battery.
In past tens year, researcher has carried out extensive research to the positive electrode of sodium-ion battery.?
In existing positive electrode system, polyanionic chemical combination objects system is considered as the sodium electricity positive electrode of most commercial promise
System.In polyanionic chemical combination objects system, NASICON type phosphate system material is logical due to having open ion diffusion
Road, excellent sodium ion conductivity, and material structure stability and thermal stability are high, great application prospect.
Currently, the NASICON type positive electrode system such as vanadium phosphate sodium, vanadium phosphate manganese sodium, titanium phosphate manganese sodium is constantly suggested,
Its excellent big multiplying power and cyclical stability have greatly pushed the development of sodium-ion battery positive material.But due to vanadium
The requirement of toxicity and continual exploitation high voltage material, so the material using fluoro system of exploitation newly has greatly meaning
Justice.
Summary of the invention
For defect problem existing for existing sodium-ion battery positive material, the first purpose of this invention is to be to mention
A kind of Na with excellent electrochemical performance is supplied3ZrMn(PO4)2F3/ C composite (present invention is also referred to as composite material,
Or positive electrode active materials).
Second object of the present invention is to provide described in one kind preparation reproducible, easy to operate, low in cost
Na3ZrMn(PO4)2F3The method of/C composite, this method have prospects for commercial application.
Third object of the present invention is to provide a kind of Na3ZrMn(PO4)2F3The application of/C composite, it is intended to be promoted
The performance of sodium-ion battery.
4th purpose of the invention is, provides a kind of sodium-ion battery positive material comprising the composite material.
5th purpose of the invention is, provides a kind of sodium-ion battery anode comprising the positive electrode.
6th purpose of the invention is, provides a kind of sodium-ion battery comprising the anode.
A kind of fluorinated phosphate zirconium manganese sodium/carbon composite is the in-situ composite of fluorinated phosphate zirconium manganese sodium, carbon, described
Fluorinated phosphate zirconium manganese sodium chemical formula be Na3ZrMn(PO4)2F3。
The present invention provides the in-situ composites of a kind of completely new chemical formula and crystal phase structure, and find that the composite material exists
There are the electric properties such as high charge-discharge specific capacity, good high rate performance and stable circulation performance in sodium-ion battery.
Preferably, the fluorinated phosphate zirconium manganese sodium/carbon composite, the mass fraction of carbon is 5~25%.
The present invention also provides fluorinated phosphate zirconium manganese sodium/carbon composite preparation method described in one kind, including it is following
Step:
Step (1): by zirconyl nitrate, manganese source, phosphorus source carry out pre-reaction, and 650~850 DEG C at a temperature of carry out first
Section sintering, is made intermediate phosphate zirconium manganese；
Step (2): being incorporated fluorine sodium raw materials and complexing agent into intermediate phosphate zirconium manganese obtained, after mixing 600~
Second segment sintering is carried out at a temperature of 750 DEG C to get the fluorinated phosphate zirconium manganese sodium/carbon composite.
The present invention innovatively provides one kind and zirconyl nitrate, manganese source, phosphorus source is converted to intermediate in advance -- basic zirconium phosphate manganese,
Then it is sintered to obtain the pre-inversion of the composite material with sodium fluorine again -- bis sintering prepares thinking.The study found that compared to existing
There is conventional one step of all materials sintering preparation thinking, innovatively pre-inversion -- bis sintering prepares thinking can using the present invention
Unexpectedly further to promote electric property of the composite material in sodium-ion battery obtained.
The present inventor is the study found that the pre-inversion -- bis sintering prepares thinking, preparation difficult point to realize the present invention
It is how successfully to realize the preparation of the intermediate phosphate zirconium manganese and how cooperates with bis sintering condition, improves product
Performance.By further investigation, present inventors have unexpectedly found that, zirconyl nitrate is limited as raw material, and the first segment is cooperated to be sintered
Temperature is precisely controlled, and can unexpectedly be made and intermediate phosphate zirconium manganese is successfully made, and can improve its crystal phase purity.
Second segment after the intermediate phosphate zirconium manganese obtained is carried out again is sintered, and electric property unexpectedly can be made more preferably
Composite material.
The research of the invention finds that using the zirconyl nitrate as raw material, the temperature for cooperating the first segment to be sintered, side
The intermediate phosphate zirconium manganese can be made, successfully so as to realize the pre-inversion bis sintering technique innovated through the invention
Promote the electric property of material obtained.
The manganese source is ionizable Mn out2+Water soluble salt, preferably manganese acetate, manganese nitrate, at least one in manganese oxalate
Kind.
Phosphorus source is the acid or water soluble salt of ionizable phosphate anion out, preferably comprises ammonium dihydrogen phosphate, phosphorus
At least one of sour hydrogen diammonium, phosphoric acid, ammonium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate.
In step (1) of the present invention, intermediate phosphate zirconium manganese is innovatively made in advance using sol-gel method.Detailed process
Such as are as follows: zirconyl nitrate, manganese source, phosphorus source are dissolved in water, obtain material solution, then carries out pre-reaction, realizes the gelation of raw material,
Then by the gel drying of acquisition, and carry out subsequent first segment sintering.
Preferably, the concentration of zirconium ion is 0.1~0.5mol L in material solution-1。
Zirconyl nitrate, manganese source, phosphorus source, fluorine sodium raw materials are 2.8~3.2:0.8~1.2 by Na, Zr, Mn, P, F molar ratio:
0.8~1.2:1.8~2.2:2.8~3.2 ratio ingredient；It is preferred that comparing ingredient by the chemical formula metering of fluorinated phosphate zirconium manganese sodium.
Preferably, the temperature of pre-reaction is 70~90 DEG C.
In step (1), it can be dried by existing means, be preferably dried in vacuo.Vacuum drying temperature example
For example 80~100 DEG C, the vacuum drying time is, for example, 3~6h.
In the present invention, to realize through the electric property of material made from the described pre-inversion bis sintering technique promotion,
Need to control the temperature of first segment sintering.
Preferably, the temperature of first segment sintering is 650~750 DEG C.The study found that at such a temperature, institute can be obtained
The intermediate phosphate zirconium manganese stated, and then be conducive to obtain high performance composite material.
The atmosphere of first segment sintering is, for example, that argon gas, nitrogen or hydrogen-argon-mixed or nitrogen are argon-mixed.
Sintering process of the invention carries out in tube furnace.
The time of first segment sintering is 8~12h.
In the present invention, innovatively it is sintered by the first segment, by zirconyl nitrate, manganese source, phosphorus source pre-conversion in
Mesosome basic zirconium phosphate manganese so carries out subsequent second segment sintering again, can further promote the electric property of material obtained.
Preferably, the fluorine sodium raw materials are sodium fluoride, or the mixture for sodium source and Fluorine source.
The sodium source can be at least one of the oxide of sodium, carbonate, nitrate, carboxylate.
The Fluorine source can be ammonium fluoride.
Preferably, the complexing agent includes at least one of citric acid, glucose, sucrose, oxalic acid, ascorbic acid.
Preferably, complexing agent and zirconyl nitrate molar ratio 2~5:1, further preferred 3:1.Control is preferably compared at this
Under example, facilitate the electric property for further promoting composite material obtained.
In the present invention, intermediate phosphate zirconium manganese, fluorine sodium raw materials and the complexing agent can be used existing method and mixed,
Preferably wet ball grinding method is mixed.More preferably scheme, the 400~600r/min of rotational speed of ball-mill, when the ball milling
Between 6~10h, most preferably 500r/min.
In the present invention, the mixture is subjected to second segment sintering, it is final to obtain the composite material.
Preferably, second segment sintering carries out under protective atmosphere.The protective atmosphere is, for example, nitrogen or inertia
Gas.
Preferably, the temperature of second segment sintering is 600~750 DEG C；Further preferably 700 DEG C.The study found that at this
Second segment sintering is carried out under preferred temperature range, helps further to cooperate with the electric property for promoting composite material obtained.
Preferably, the time of second segment sintering is 8~16h；Further preferably 8~10h.
Na of the invention3ZrMn(PO4)2F3The preparation method of/C composite, comprising the following specific steps
A: by zirconyl nitrate, manganese source, phosphorus source is dissolved in deionized water, is placed in stirring evaporation at 70~90 DEG C and is formed and is coagulated
Glue.
B: by gel to 80~100 degree in a vacuum drying oven, then dry 3~6h carries out it under protective atmosphere
650~850 degree of 8~12h of burning, obtain intermediate phosphate zirconium manganese；
C: by obtained intermediate phosphate zirconium manganese with certain proportion and sodium fluoride, complexing agent mixes 400~600r/min ball
6~10h is ground, then 600~750 degree of 8~16h of sintering under an ar atmosphere.
The invention also includes using Na made from the preparation method3ZrMn(PO4)2F3/ C composite.
Na of the invention3ZrMn(PO4)2F3/ C composite is that (NASICON is brilliant for Fast ion conductor type crystal structure
Type).
The present invention also provides a kind of Na3ZrMn(PO4)2F3The application of/C composite, is used as sodium-ion battery
Positive electrode active materials.
Preferred application, by the Na3ZrMn(PO4)2F3/ C composite and binder, conductive agent mixing pulp apply
It covers on a current collector, solidification obtains sodium-ion battery anode.
The anode is assembled into sodium-ion battery by further preferred application.
The present invention also provides a kind of sodium-ion battery positive materials, and it includes the fluorinated phosphate zirconium manganese sodium/carbon is multiple
Condensation material (sodium-ion battery positive electrode active materials).
It preferably, also include binder and conductive agent in the positive electrode.The binder can be led for sodium electricity
Field technique personnel can be obtained material arbitrarily with cementation, such as PVDF.The conductive agent can be led for sodium electricity
Field technique personnel can be obtained the material arbitrarily with enhancing conducting function, such as conductive black.
In the positive electrode, positive electrode active materials, binder and conductive agent can occupy sodium electrical domain use demand into
Row adjustment.
The present invention also provides a kind of sodium-ion battery anodes, include collector, and be compounded in the institute of collection liquid surface
The sodium-ion battery positive material stated.
The collector can be the positive carrier material for any positive electrode that can be known in sodium electricity industry, such as
For aluminium foil.
The present invention is by Na3ZrMn(PO4)2F3/ C composite positive pole be used to prepare sodium-ion battery anode method with
And it is as follows to the method for its electrochemical property test.
For example, by the Na3ZrMn(PO4)2F3After/C composite is mixed with conductive agent and binder, pass through coating
On aluminium foil, sodium-ion battery anode is made.Used conductive agent, binder can be used well-known to those skilled in the art
Material.The method of assembling preparation sodium-ion battery positive material is see also existing method.
For example, Na is made in the present invention3ZrMn(PO4)2F3/ C composite conductive black and PVDF binder are according to 8:1:1
Mass ratio ground, after being sufficiently mixed be added NMP form uniform slurry, be coated in aluminium foil on as test electricity
Pole, using metallic sodium as to electrode, electrolyte is 1M NaClO4/ 100% PC prepares sodium half-cell and tests its electrochemistry
Energy.
The present invention also provides a kind of sodium-ion batteries, are anode with the sodium-ion battery anode.
The structure of the sodium-ion battery can refer to the structure that can be known in industry, and the main distinction is, using packet
Anode containing the positive electrode active materials that the present invention innovates.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
1) the invention proposes a kind of completely new Na3ZrMn(PO4)2F3/ C composite, and find that it possesses open frame
Structure is conducive to the fast transferring of sodium ion, and has high voltage, the characteristic of high specific discharge capacity and good thermostabilization
Property.Na of the invention3ZrMn(PO4)2F3/ C composite is used for sodium-ion battery as positive electrode, shows to have excellent
Chemical property, voltage is high, stable cycle performance, and system material is environment-protecting and non-poisonous.
2) one kind proposed by the present invention can successfully synthesize the Na3ZrMn(PO4)2F3The method of/C composite, and innovate
Ground discovery, using zirconyl nitrate, manganese source, phosphorus source are converted to intermediate in advance -- basic zirconium phosphate manganese, then again with the sintering of sodium fluorine
Preparing material made from thinking has more preferably electric property.
3) it has also been found that, thinking is prepared for the pretreatment bis sintering described in successfully realizing, it can be by using nitric acid
Oxygen zirconium is raw material, cooperates the Collaborative Control of sintering temperature, can successfully obtain the intermediate, and then is conducive to cooperate subsequent
Sintering promotes the electric property of composite material obtained.
Detailed description of the invention
Fig. 1 is Na3ZrMn(PO4)2F3The XRD diagram of/C；
Fig. 2 is Na3ZrMn(PO4)2F3The SEM of/C schemes.
Specific embodiment
Following embodiment is intended to be described in further details the content of present invention；And the protection scope of the claims in the present invention
It is not limited by the example.
Embodiment 1
0.01mol zirconyl nitrate and 0.01mol manganese acetate are taken, the ammonium dihydrogen phosphate of 0.02mol is dissolved in deionized water,
Stirring evaporation forms gel under 80 degree, gel is placed in 80 degree of vacuum oven and dries 4h, then put it into and be connected with
In the tube furnace of argon gas, 750 degree of sintering 10h.Obtain intermediate phosphate zirconium manganese, by basic zirconium phosphate manganese intermediate and sodium fluoride by mole
It is mixed than 1:3, the citric acid of 0.03mol is added.500r/min ball milling 8h, 700 degree of sintering 12h under the conditions of argon gas.To obtain the final product
Na3ZrMn(PO4)2F3/ C, xrd such as Fig. 1, sem, Fig. 2.
Utilize Na obtained3ZrMn(PO4)2F3/ C composite is assembled into sodium ion button cell, measures electrochemistry number
According to having, average voltage 4.0V recycles its specific discharge capacity after 100 circles at 0.5C and reaches 90.5mAh/g, and capacity retention ratio is up to 95%
More than.
Embodiment 2
0.01mol zirconyl nitrate and 0.01mol manganese acetate are taken, the ammonium dihydrogen phosphate of 0.02mol is dissolved in deionized water,
Stirring evaporation forms gel under 80 degree, gel is placed in 80 degree of vacuum oven and dries 4h, then put it into and be connected with
In the tube furnace of argon gas, 650 degree of sintering 8h.Obtain intermediate phosphate zirconium manganese, by intermediate phosphate zirconium manganese and sodium fluoride by mole
It is mixed than 1:3, the citric acid of 0.03mol is added.500r/min ball milling 8h, 700 degree of sintering 12h under the conditions of argon gas.To obtain the final product
Na3ZrMn(PO4)2F3/C。
Utilize Na obtained3ZrMn(PO4)2F3/ C composite is assembled into sodium ion button cell, measures electrochemistry number
According to having, average voltage 4.0V recycles its specific discharge capacity after 100 circles at 0.5C and reaches 87.5mAh/g, and capacity retention ratio is up to 90%
More than.
Embodiment 3
0.01mol zirconyl nitrate and 0.01mol manganese acetate are taken, the ammonium dihydrogen phosphate of 0.02mol is dissolved in deionized water,
Stirring evaporation forms gel under 80 degree, gel is placed in 80 degree of vacuum oven and dries 4h, then put it into and be connected with
In the tube furnace of argon gas, 850 degree of sintering 16h.Obtain intermediate phosphate zirconium manganese, by intermediate phosphate zirconium manganese and sodium fluoride by mole
It is mixed than 1:3, the citric acid of 0.03mol is added.500r/min ball milling 8h, 700 degree of sintering 12h under the conditions of argon gas.To obtain the final product
Na3ZrMn(PO4)2F3/C。
Utilize Na obtained3ZrMn(PO4)2F3/ C composite is assembled into sodium ion button cell, measures electrochemistry number
According to having, average voltage 4.0V recycles its specific discharge capacity after 100 circles at 0.5C and reaches 84.5mAh/g, and capacity retention ratio is up to 90%
More than.
Embodiment 4
0.01mol zirconyl nitrate and 0.01mol manganese acetate are taken, the ammonium dihydrogen phosphate of 0.02mol is dissolved in deionized water,
Stirring evaporation forms gel under 80 degree, gel is placed in 80 degree of vacuum oven and dries 4h, then put it into and be connected with
In the tube furnace of argon gas, 750 degree of sintering 10h.Obtain intermediate phosphate zirconium manganese, by intermediate phosphate zirconium manganese and sodium fluoride by mole
It is mixed than 1:3, the citric acid of 0.03mol is added.500r/min ball milling 8h, 700 degree of sintering 16h under the conditions of argon gas.To obtain the final product
Na3ZrMn(PO4)2F3/C。
Utilize Na obtained3ZrMn(PO4)2F3/ C composite is assembled into sodium ion button cell, measures electrochemistry number
According to having, average voltage 4.0V recycles its specific discharge capacity after 100 circles at 0.5C and reaches 87.5mAh/g, and capacity retention ratio is up to 90%
More than.
Embodiment 5
0.01mol zirconyl nitrate and 0.01mol manganese acetate are taken, the ammonium dihydrogen phosphate of 0.02mol is dissolved in deionized water,
Stirring evaporation forms gel under 80 degree, gel is placed in 80 degree of vacuum oven and dries 4h, then put it into and be connected with
In the tube furnace of argon gas, 750 degree of sintering 10h.Obtain intermediate phosphate zirconium manganese, by intermediate phosphate zirconium manganese and sodium fluoride by mole
It is mixed than 1:3, the citric acid of 0.03mol is added.500r/min ball milling 8h, 600 degree of sintering 8h under the conditions of argon gas.To obtain the final product
Na3ZrMn(PO4)2F3/C。
Utilize Na obtained3ZrMn(PO4)2F3/ C composite is assembled into sodium ion button cell, measures electrochemistry number
According to having, average voltage 4.0V recycles its specific discharge capacity after 100 circles at 0.5C and reaches 83.1mAh/g, and capacity retention ratio is up to 88%
More than.
Embodiment 6
0.01mol zirconyl nitrate and 0.01mol manganese acetate are taken, the ammonium dihydrogen phosphate of 0.02mol is dissolved in deionized water,
Stirring evaporation forms gel under 80 degree, gel is placed in 100 degree of vacuum oven and dries 4h, then put it into logical
Have in the tube furnace of argon gas, 750 degree of sintering 10h.Intermediate phosphate zirconium manganese is obtained, intermediate phosphate zirconium manganese and sodium fluoride are massaged
You mix than 1:3, and the citric acid of 0.03mol is added.500r/min ball milling 8h, 700 degree of sintering 12h under the conditions of argon gas.To obtain the final product
Na3ZrMn(PO4)2F3/C。
Utilize Na obtained3ZrMn(PO4)2F3/ C composite is assembled into sodium ion button cell, measures electrochemistry number
According to having, average voltage 4.0V recycles its specific discharge capacity after 100 circles at 0.5C and reaches 87.6mAh/g, and capacity retention ratio is up to 90%
More than.
Embodiment 7
0.01mol zirconyl nitrate and 0.01mol manganese acetate are taken, the ammonium dihydrogen phosphate of 0.02mol is dissolved in deionized water,
Stirring evaporation forms gel under 80 degree, gel is placed in 80 degree of vacuum oven and dries 4h, then put it into and be connected with
In the tube furnace of argon gas, 750 degree of sintering 10h.Obtain intermediate phosphate zirconium manganese, by intermediate phosphate zirconium manganese and sodium fluoride by mole
It is mixed than 1:3, the citric acid of 0.05mol is added.500r/min ball milling 8h, 700 degree of sintering 12h under the conditions of argon gas.To obtain the final product
Na3ZrMn(PO4)2F3/C。
Utilize Na obtained3ZrMn(PO4)2F3/ C composite is assembled into sodium ion button cell, measures electrochemistry number
According to having, average voltage 4.0V recycles its specific discharge capacity after 100 circles at 0.5C and reaches 86.4mAh/g, and capacity retention ratio is up to 90%
More than.
Comparative example 1
It is compared with embodiment 1, difference is, zirconyl nitrate replaced using conventional zirconates, is characterized in particular in:
0.01mol acetylacetone,2,4-pentanedione zirconium and 0.01 manganese acetate are taken, the ammonium dihydrogen phosphate of 0.02mol is dissolved in deionized water,
80 degree of lower stirring evaporations can not obtain intermediate.
Comparative example 2
It is compared with embodiment, difference is, the dosage of citric acid is lower, specifically:
0.01mol zirconyl nitrate and 0.01mol manganese acetate are taken, the ammonium dihydrogen phosphate of 0.02mol is dissolved in deionized water,
Stirring evaporation forms gel under 80 degree, gel is placed in 80 degree of vacuum oven and dries 4h, then put it into and be connected with
In the tube furnace of argon gas, 750 degree of sintering 10h.Obtain intermediate phosphate zirconium manganese, by intermediate phosphate zirconium manganese and sodium fluoride by mole
It is mixed than 1:3, the citric acid of 0.01mol is added.500r/min ball milling 8h, 700 degree of sintering 12h under the conditions of argon gas.
Obtained composite material carries out the test such as embodiment 1, as a result are as follows: average voltage 4.0V is recycled at 0.5 C
It is only 70% that its specific discharge capacity, which reaches 73.6mAh/g. capacity retention ratio, after 100 circles.
Comparative example 3
Compared with embodiment, difference is, first segment sintering temperature exceed the present invention claims range, specifically:
0.01mol zirconyl nitrate and 0.01mol manganese acetate are taken, the ammonium dihydrogen phosphate of 0.02mol is dissolved in deionized water,
Stirring evaporation forms gel under 80 degree, gel is placed in 80 degree of vacuum oven and dries 4h, then put it into and be connected with
In the tube furnace of argon gas, 950 degree of sintering 10h.1:3 is mixed in molar ratio for the sinter and sodium fluoride, and the lemon of 0.03mol is added
Lemon acid.500r/min ball milling 8h, 700 degree of sintering 12h under the conditions of argon gas.Useful activity substance is not obtained.
Comparative example 4
Compared with embodiment, difference is, second segment sintering temperature exceed the present invention claims range, specifically:
0.01mol zirconyl nitrate and 0.01mol manganese acetate are taken, the ammonium dihydrogen phosphate of 0.02mol is dissolved in deionized water,
Stirring evaporation forms gel under 80 degree, gel is placed in 80 degree of vacuum oven and dries 4h, then put it into and be connected with
In the tube furnace of argon gas, 750 degree of sintering 10h.Obtain intermediate phosphate zirconium manganese, by intermediate phosphate zirconium manganese and sodium fluoride by mole
It is mixed than 1:3, the citric acid of 0.03mol is added.500r/min ball milling 8h, 800 degree of sintering 12h under the conditions of argon gas.
Obtained composite material carries out the test such as embodiment 1, as a result are as follows: average voltage 4.0V is recycled at 0.5 C
Its specific discharge capacity reaches 61.2mAh/g after 100 circles.
Comparative example 5 (not fluorine-containing material)
It is compared with embodiment, difference is, active material of the invention is not obtained, specifically: take 0.01mol Nitric Acid Oxidation
Zirconium and 0.01 manganese acetate, the ammonium dihydrogen phosphate of 0.02mol are dissolved in deionized water, and stirring evaporation forms gel under 80 degree, will
Gel is placed in 80 degree of vacuum oven and dries 4h, then puts it into the tube furnace for being connected with argon gas, 750 degree of sintering 10h.
Intermediate phosphate zirconium manganese is obtained, by intermediate phosphate zirconium manganese, 2:3 is mixed sodium carbonate in molar ratio, and the lemon of 0.03mol is added
Acid.500r/min ball milling 8h, 700 degree of sintering 12h under the conditions of argon gas.
Obtained composite material carries out the test such as embodiment 1, as a result are as follows: average voltage 3.7V is recycled at 0.5 C
Its specific discharge capacity reaches 79mAh/g after 100 circles, and capacity retention ratio is up to 87% or more.
Comparative example 6:
It is compared with embodiment 1, difference is, non-pre-conversion is at intermediate, direct one-stage sintering, specifically:
It is compared with embodiment 1, difference is only that, by each raw material of synthesis 700 under the conditions of 500r/min ball milling 8h, argon gas
Degree sintering 12h.The electric property of the obtained composite material of test, its specific discharge capacity reaches after 100 circles are recycled at 0.5C
47mAh/g, capacity retention ratio are only 70%.
Claims (10)
1. a kind of fluorinated phosphate zirconium manganese sodium/carbon composite, which is characterized in that for fluorinated phosphate zirconium manganese sodium, the In-situ reaction of carbon
Material, the chemical formula of the fluorinated phosphate zirconium manganese sodium are Na3ZrMn(PO4)2F3。
2. fluorinated phosphate zirconium manganese sodium/carbon composite as described in claim 1, which is characterized in that the mass fraction of carbon be 5~
25%.
3. a kind of preparation method of fluorinated phosphate zirconium manganese sodium/carbon composite of any of claims 1 or 2, which is characterized in that packet
Include following steps:
Step (1): zirconyl nitrate, manganese source, phosphorus source are subjected to pre-reaction, and in 650~850 DEG C of at a temperature of progress first segment burning
Intermediate phosphate zirconium manganese is made in knot；
Step (2): fluorine sodium raw materials and complexing agent are incorporated into intermediate phosphate zirconium manganese obtained, at 600~750 DEG C after mixing
At a temperature of carry out second segment sintering to get the fluorinated phosphate zirconium manganese sodium/carbon composite.
4. the preparation method of fluorinated phosphate zirconium manganese sodium/carbon composite as claimed in claim 3, which is characterized in that
The manganese source is ionizable Mn out2+Water soluble salt, preferably manganese acetate, manganese nitrate, at least one of manganese oxalate；
Phosphorus source is the acid or water soluble salt of ionizable phosphate anion out, preferably comprises ammonium dihydrogen phosphate, phosphoric acid hydrogen
At least one of diammonium, phosphoric acid, ammonium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate；
Preferably, the temperature of pre-reaction is 70~90 DEG C.
5. the preparation method of fluorinated phosphate zirconium manganese sodium/carbon composite as claimed in claim 3, which is characterized in that described
Fluorine sodium raw materials are sodium fluoride, or the mixture for sodium source and Fluorine source；
The sodium source can be at least one of the oxide of sodium, carbonate, nitrate, carboxylate；
The Fluorine source can be ammonium fluoride；
The complexing agent includes at least one of citric acid, glucose, sucrose, oxalic acid, ascorbic acid；
Zirconyl nitrate, manganese source, phosphorus source, fluorine sodium raw materials by Na, Zr, Mn, P, F molar ratio be 2.8~3.2:0.8~1.2:0.8~
The ratio ingredient of 1.2:1.8~2.2:2.8~3.2；It is preferred that comparing ingredient by the chemical formula metering of fluorinated phosphate zirconium manganese sodium；
2~5:1 of complexing agent and zirconyl nitrate molar ratio.
6. the preparation method of fluorinated phosphate zirconium manganese sodium/carbon composite as claimed in claim 3, which is characterized in that second segment
Sintering carries out under protective atmosphere；
The time of second segment sintering is 8~16h.
7. a kind of described in any item fluorinated phosphate zirconium manganese sodium/carbon composites of claim 1~2 or claim 3~6
Fluorinated phosphate zirconium manganese sodium/carbon composite application made from any one preparation method, which is characterized in that be used as sodium
The positive electrode active materials of ion battery；
Preferably, by itself and binder, conductive agent mixing pulp, on a current collector, solidification obtains sodium-ion battery anode for coating；
Further preferably, the anode is assembled into sodium-ion battery.
8. a kind of sodium-ion battery positive material, which is characterized in that described in any item comprising claims requirement 1~2
Fluorinated phosphate zirconium made from any one of fluorinated phosphate zirconium manganese sodium/carbon composite or claim 3~6 preparation method
Manganese sodium/carbon composite；
It preferably, also include binder and conductive agent.
9. a kind of sodium-ion battery anode, which is characterized in that include collector, and be compounded in the claim of collection liquid surface
Sodium-ion battery positive material described in 8.
10. a kind of sodium-ion battery, which is characterized in that with sodium-ion battery anode as claimed in claim 9 be anode.
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