CN106981641A - A kind of carbon coating titanium phosphate manganese sodium composite and preparation method thereof and the application in sodium-ion battery - Google Patents
A kind of carbon coating titanium phosphate manganese sodium composite and preparation method thereof and the application in sodium-ion battery Download PDFInfo
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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
- H01M4/366—Composites as layered products
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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
- H01M4/36—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
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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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- 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
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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 discloses a kind of Na3MnTi(PO4)3/ C composite and preparation method thereof and the application in sodium-ion battery, the composite is to coat Na by carbon-coating3MnTi(PO4)3Particle is constituted；Its synthetic method is to serve as reducing agent and carbon source using organic matter, using cheap manganese source, titanium source as raw material, has the carbon coating Na of excellent properties by Solid phase synthesis3MnTi(PO4)3Composite positive pole, the preparation method is simple and easy to apply, mild condition, and yield is high, when the composite of preparation is applied as sodium-ion battery positive material, shows high-energy-density, high working voltage, good stable circulation performance and excellent high rate performance.
Description
Technical field
The present invention relates to a kind of sodium ion positive electrode, more particularly to a kind of carbon coating Na3MnTi(PO4)3What is constituted is compound
Material and synthesis in solid state Na3MnTi(PO4)3/ C method, and Na3MnTi(PO4)3/ C should as sodium ion positive electrode
With belonging to sodium-ion battery field.
Background technology
As lithium ion battery has achieved fast development in 3C Product and electric automobiles, and show good hair
While exhibition prospect, because metal lithium resource is in the scarcity of crustal abundance, lithium ion battery is difficult to meet in large-scale energy storage field
In large-scale application, its manufacturing cost also will be in the trend that constantly rises with the scarcity of lithium resource.Compared with elemental lithium, sodium member
Element rich reserves and source is more extensive in the earth's crust, and sodium element is in same main group with lithium in the periodic table of elements, so
There is similar physicochemical property to lithium.Therefore, the manufacturing cost of relative moderate and the sodium ion electricity compared favourably with lithium ion battery
Pond turns into a kind of usable battery system of storage on a large scale of most potential achievable industry.However, due to the ion of sodium ion
Radius is bigger than the ionic radius of lithium ion so that in kinetically sodium ion, lithium ion is compared in embedded and abjection in electrode material
It is more difficult, and sodium ion is with respect to the oxidation-reduction potential and larger atomic mass of calibration so that sodium-ion battery positive pole material
The low voltage of material, energy density is not high.Therefore, improve sodium-ion battery positive material voltage and turning into for energy density is studied
Emphasis.
It is similar with lithium ion battery, in sodium-ion battery positive material polyanionic system, Na2Fe2(SO4)3Have
3.8V theoretical plates, with the platform compared favourably with lithium ion battery but because there is sulfate system hygroscopicity easily to cause
Material surface poisoning effect, result in the problems such as material preparation process requires harsh to production environment, material property is unstable.Phosphorus
Silicate system has three-dimensional crystalline structure, and with good heat endurance and electrochemical stability, but the voltage of material is relative
It is relatively low in sulfate system.By design it is phosphatic in transition metal, can regulate and control phosphate system voltage put down
Platform, so as to obtain high-tension positive electrode.Vanadium phosphate sodium positive electrode has 3.4V operating voltage, but is due to pentavalent vanadium
To environment and the damaging effect of human body, application is environmentally safe on a large scale has very important side effect, also, vanadium source phase
Expensive for manganese, titanium source, crustal abundance is low, and raw material sources are few.
The content of the invention
The defect existed for existing sodium-ion battery positive material, the purpose of the present invention is to be to provide a kind of cladding
Uniformly, property stabilization, the Na that crystalline phase is single and electro-chemical activity is high3MnTi(PO4)3/ C composite.
Another object of the present invention is to provide a kind of mild condition, preparation Na simple to operate, with low cost3MnTi
(PO4)3The method of/C composite, this method is easily achieved large-scale production.
Third object of the present invention is to be to provide the Na3MnTi(PO4)3/ C composite is applied and is used as sodium ion
The application of cell positive material, sodium-ion battery show high-energy-density, high working voltage, good stable circulation performance with
And excellent high rate performance.
In order to realize above-mentioned technical purpose, the invention provides a kind of Na3MnTi(PO4)3/ C composite, it is by carbon bag
Cover Na3MnTi(PO4)3Particle is constituted.Technical scheme produces carbon original position by organic matter pyrolysis and is evenly coated at
Na4MnTi(PO4)3Particle surface, makes Na3MnTi(PO4)3Material has more excellent electric conductivity, between material and electrolyte
Contact interface more stablize, coulombic efficiency is higher, and electrode side reaction is few.
It is preferred that scheme, Na3MnTi(PO4)3Grain diameter is 100~2000nm.
It is preferred that scheme, Na3MnTi(PO4)3The carbon coating layer thickness of particle is 5~50nm.
It is preferred that scheme, Na3MnTi(PO4)3With trigonal system, space group isWith the crystal structure
Na4MnTi(PO4)3For NASICON (fast-ionic conductor) type, the quick transmission of sodium ion can be realized, so that with good multiplying power
Performance.
The invention provides described Na3MnTi(PO4)3The preparation method of/C composite, the preparation method is by sodium
After source, phosphorus source, titanium source, manganese source and carbon source ball milling mixing, it is placed in protective atmosphere, is first warming up to 300~400 DEG C of sintering, then rise
Temperature is produced to 500~900 DEG C of sintering.
It is preferred that scheme, sodium source, phosphorus source, the consumption of titanium source and manganese source press Na:P:Ti:Mn mol ratio is 2.6~3.4:
3:0.8~1.2:0.8~1.2.More preferably 2.6~3.25:3:1:1.
It is preferred that scheme, the consumption of the carbon source for generation Na3MnTi(PO4)3The 5% of/C composite quality~
300%；More preferably 5%~150%.The consumption of carbon source decides the thickness of carbon coating layer, and coating thickness is in suitable model
In enclosing, be conducive to obtaining that stability is good, electrochemical performance Na3MnTi(PO4)3/ C composite.
More preferably scheme, the sodium source is general using sodium as the compound of cation, mainly including sodium carbonate, bicarbonate
In sodium, sodium acetate, sodium oxalate, sodium nitrate, sodium sulphate, niter cake, sodium citrate, sodium hydroxide, sodium nitrate, sodium oxalate at least
It is a kind of.The more preferably Organic Sodium Salt such as sodium oxalate.
More preferably scheme, phosphorus source includes ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, disodium hydrogen phosphate, di(2-ethylhexyl)phosphate
At least one of hydrogen sodium.More preferably ammonium dihydrogen phosphate.
More preferably scheme, the titanium source includes at least one of titanium dioxide, titanyl sulfate, titanium sulfate.More preferably
Titanium dioxide.
More preferably scheme, the manganese source includes manganese monoxide, manganese dioxide, mangano-manganic oxide, manganese sulfate, protochloride
At least one of manganese, manganese oxalate, manganese nitrate.
More preferably scheme, the carbon source includes glucose, starch, citric acid, ascorbic acid, polyvinyl alcohol, polyoxygenated
At least one in ethene, poly-dopamine, polyacrylonitrile, poly-dopamine, polyvinylpyrrolidone, CNT, carbon fiber, graphene
Kind.Carbon source is mainly as Na3MnTi(PO4)3Clad raw material, while being used as reducing agent.
It is preferred that scheme, the condition of the ball milling is：Ball material mass ratio is 30~100:1；Engine speed be 300~
1600r/min, Ball-milling Time is 6~48h.Preferred ball material mass ratio is 50~70:1.Engine speed is more preferably 500~
1000r/min, Ball-milling Time is more preferably 10~14h.
It is preferred that scheme, described ball milling carries out in organic media.More preferably acetone, absolute ethyl alcohol etc., these have
Machine solvent has more preferable wetability to various solid principles, ball milling mixing effect is improved, so as to obtain the more preferable product of purity.
It is preferred that scheme, after sodium source, phosphorus source, titanium source, manganese source and carbon source ball milling mixing, done at a temperature of being placed in 80~120 DEG C
It is dry, 100~400 mesh sieves are crossed, take minus sieve powder to be sintered.
It is preferred that scheme, be 0~12h in the times of 300~400 DEG C of sintering, 500~900 DEG C of sintering times for 6~
24h, heating rate is 2~10 DEG C/min.By controlling sintering temperature and time and heating rate, it is less to obtain dephasign, knot
It is brilliant complete, the moderate Na of particle size3MnTi(PO4)3/ C composite, be conducive to improve composite electric conductivity and other
Electric property.
The protective atmosphere of the present invention can be high pure nitrogen or high-purity argon gas or their mixed gas.
Present invention also offers described Na3MnTi(PO4)3The application of/C composite, as sodium ion positive pole material
Material application.
The Na of the present invention3MnTi(PO4)3/ C composite is as sodium-ion battery positive material application, using existing method
To be assembled into sodium-ion battery, and its performance is tested：Weigh above-mentioned Na3MnTi(PO4)3/ C composite, is added
10wt.% conductive carbon blacks are as conductive agent, and 10wt.%PVDF is ground fully to add a small amount of NMP mixing afterwards as binding agent
Uniform black paste slurry is formed, these slurries is coated in aluminum foil current collector as test electrode, made with metallic sodium piece
Button cell is assembled into for comparison electrode, it uses electrolyte system for 1M NaClO4/PC.Filled used in test loop performance
Discharge current density is 100mAh g-1(1C multiplying powers).
Compared with prior art, the advantageous effects that technical scheme is brought：
The Na of the present invention3MnTi(PO4)3/ C composite has special carbon coating structure, makes Na3MnTi(PO4)3Material
Stability is improved, electric conductivity increase, improves its electro-chemical activity.
The Na of the present invention3MnTi(PO4)3Active material Na in/C composite3MnTi(PO4)3Tripartite with high-purity
Phase, stability is good, and electro-chemical activity is high.
The Na of the present invention3MnTi(PO4)3/ C composite uses Solid phase synthesis, using ball milling mixing combination sinter molding
Method synthesis Na3MnTi(PO4)3/ C composite, improves the contact between solid material by high-energy ball milling, makes reaction
More fully, the generation of impurities phase is reduced, is molded by the method for step sintering, is conducive to improving plane of crystal performance, improves
Crystal perfection, while improving being evenly coated property, granular size homogeneity.
The Na of the present invention3MnTi(PO4)3Na in the preparation method of/C composite3MnTi(PO4)3With the generation of carbon, and
Carbon is to Na3MnTi(PO4)3Cladding, the one-step shaping in sintering process enormously simplify processing step.
The Na of the present invention3MnTi(PO4)3/ C composite has good high rate performance and excellent cycle performance, 3.6V
Make material that there is higher power density with two discharge platforms of 4.1V.
The Na of the present invention3MnTi(PO4)3The preparation process of/C composite uses cheap sodium source, phosphorus source, titanium source, manganese source
And carbon source is prepared for pure phase Na as raw material by solid-phase ball milling3MnTi(PO4)3/ C composite, reduces cost.
The Na of the present invention3MnTi(PO4)3/ C composite is evenly coated, and cladding thickness is moderate, and cladding means are simple.
The Na of the present invention3MnTi(PO4)3When/C composite is applied as sodium-ion battery positive material, high energy is shown
Metric density, high working voltage, good stable circulation performance and excellent high rate performance.
Brief description of the drawings
【Fig. 1】It is Na prepared by embodiment 13MnTi(PO4)3The X-ray diffractogram of/C composite；
【Fig. 2】It is Na prepared by embodiment 13MnTi(PO4)3The scanning electron microscope (SEM) photograph of/C composite；
【Fig. 3】It is Na prepared by embodiment 13MnTi(PO4)3Cyclic curve figure under the 1C of/C composite.
Embodiment
Following examples are intended to be described in further details present invention；And the protection domain of the claims in the present invention
It is not limited by the example.
Embodiment 1
The present embodiment comprises the following steps：
Step (1)：The present embodiment design generation 0.03mol target products Na3MnTi(PO4)3/ C composite, will
0.045mol sodium oxalates, 0.09mol ammonium dihydrogen phosphates, 0.03mol titanium dioxide, 0.03mol manganese dioxide, 1.45g glucose,
1400g zirconium oxide ball milling pearls are added, a certain amount of acetone is added and is used as abrasive media；
Step (2)：The ball milling 12h under rotating speed 800r/min, is placed in 80 DEG C of baking ovens and dries, and 200 mesh are crossed after crushing grinding
Sieve, obtains Na3MnTi(PO4)3/ C composite presoma；
Step (3)：Presoma obtained by step (2) is sintered into 6h under 350 DEG C, high-purity argon gas atmosphere, then is warming up to 650
DEG C sintering 12h, programming rate：5 DEG C/min, Na can be obtained after natural cooling3MnTi(PO4)3/ C composite；
Button cell is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece, its material list
Chemical property seek peace as shown in the figure：
Fig. 1 shows to successfully synthesize Na3MnTi(PO4)3/ C composite.
The Na of the visible synthesis of Fig. 23MnTi(PO4)3/ C composite, particle diameter distribution is uniform, and average grain diameter is 1000nm, carbon
Coating thickness is 8nm.
Fig. 3 is Na3MnTi(PO4)3/ C composite is assembled into button cell specific discharge capacity under 1C multiplying powers with sodium piece
80mAh g-1, after 100 circle circulations, discharge capacity still maintains 67mAh g-1。
Embodiment 2
The present embodiment comprises the following steps：
Step (1)：The present embodiment design generation 0.03mol target products Na3MnTi(PO4)3/ C composite, will
0.047mol sodium oxalates, 0.09mol ammonium dihydrogen phosphates, 0.03mol titanium dioxide, 0.03mol manganese dioxide, 1.45g glucose,
1400g zirconium oxide ball milling pearls are added, a certain amount of acetone is added and is used as abrasive media；
Step (2)：The ball milling 24h under rotating speed 1000r/min, is placed in 80 DEG C of baking ovens and dries, excessively 100 after crushing grinding~
400 mesh sieves, obtain Na4MnTi(PO4)3/ C composite presoma；
Step (3)：Presoma obtained by step (2) is sintered into 6h under 350 DEG C, high-purity argon gas atmosphere, then is warming up to 750
DEG C sintering 12h, programming rate：5 DEG C/min, Na can be obtained after natural cooling3MnTi(PO4)3/ C composite；
The battery assembling of the present embodiment resulting materials and method of testing are same as Example 1, Na3MnTi(PO4)3/ C is combined
Material average grain diameter is 1000nm, and carbon coating layer thickness is 9nm.Specific discharge capacity is 82mAh g under 1C multiplying powers-1, 100 circle follow
After ring, discharge capacity still maintains 65mAh g-1。
Embodiment 3
The present embodiment comprises the following steps：
Step (1)：The present embodiment design generation 0.03mol target products Na3MnTi(PO4)3/ C composite, will
0.043mol sodium oxalates, 0.09mol ammonium dihydrogen phosphates, 0.03mol titanium dioxide, 0.03mol manganese dioxide, 1.45g starch, plus
Enter 1400g zirconium oxide ball milling pearls, add a certain amount of acetone and be used as abrasive media；
Step (2)：The ball milling 48h under rotating speed 1600r/min, is placed in 80 DEG C of baking ovens and dries, excessively 100 after crushing grinding~
400 mesh sieves, obtain Na4MnTi(PO4)3/ C composite presoma；
Step (3)：Presoma obtained by step (2) is sintered into 8h under 400 DEG C, high-purity argon gas atmosphere, then heated up 700 DEG C
Sinter 18h, programming rate：5 DEG C/min, Na can be obtained after natural cooling3MnTi(PO4)3/ C composite；
The battery assembling of the present embodiment resulting materials and method of testing are same as Example 1, Na3MnTi(PO4)3/ C is combined
Material average grain diameter is 1200nm, and carbon coating layer thickness is 10nm.Specific discharge capacity is 76mAh g under 1C multiplying powers-1, 100 circles
After circulation, discharge capacity still maintains 63mAh g-1。
Embodiment 4
The present embodiment comprises the following steps：
Step (1)：The present embodiment design generation 0.03mol target products Na3MnTi(PO4)3/ C composite, will
0.045mol sodium carbonate, 0.09mol diammonium hydrogen phosphates, 0.028mol titanium dioxide, 0.03mol manganese dioxide, 1.45g grapes
Sugar, adds 1400g zirconium oxide ball milling pearls, adds a certain amount of acetone and is used as abrasive media；
Step (2)：The ball milling 24h under rotating speed 1000r/min, is placed in 80 DEG C of baking ovens and dries, excessively 100 after crushing grinding~
400 mesh sieves, obtain Na4MnTi(PO4)3/ C composite presoma；
Step (3)：Presoma obtained by step (2) is sintered into 6h under 350 DEG C, high-purity argon gas atmosphere, then is warming up to 750
DEG C sintering 12h, programming rate：5 DEG C/min, Na can be obtained after natural cooling3MnTi(PO4)3/ C composite；
The battery assembling of the present embodiment resulting materials and method of testing are same as Example 1, Na3MnTi(PO4)3/ C is combined
Material average grain diameter is 1000nm, and carbon coating layer thickness is 8nm.Specific discharge capacity is 84mAh g under 1C multiplying powers-1, 100 circle follow
After ring, discharge capacity still maintains 63mAh g-1。
Embodiment 5
The present embodiment comprises the following steps：
Step (1)：The present embodiment design generation 0.03mol target products Na3MnTi(PO4)3/ C composite, will
0.045mol sodium carbonate, 0.09mol diammonium hydrogen phosphates, 0.03mol titanium dioxide, 0.03mol manganese dioxide, 1.45g glucose,
1400g zirconium oxide ball milling pearls are added, a certain amount of acetone is added and is used as abrasive media；
Step (2)：The ball milling 24h under rotating speed 1000r/min, is placed in 80 DEG C of baking ovens and dries, excessively 100 after crushing grinding~
400 mesh sieves, obtain Na4MnTi(PO4)3/ C composite presoma；
Step (3)：By the presoma high-purity argon gas atmosphere obtained by step (2), 12h, programming rate are sintered at 750 DEG C：5
DEG C/min, Na can be obtained after natural cooling3MnTi(PO4)3/ C composite；
The battery assembling of the present embodiment resulting materials and method of testing are same as Example 1, Na3MnTi(PO4)3/ C is combined
Material average grain diameter is 1000nm, and carbon coating layer thickness is 9nm.Specific discharge capacity is 82mAh g under 1C multiplying powers-1, 100 circle follow
After ring, discharge capacity still maintains 61mAh g-1。
Comparative example 1
Starting material element content is adjusted to Na:P:Ti:Mn mol ratio is 3.8:3:1:1
Step (1)：The present embodiment design generation 0.03mol target products Na3MnTi(PO4)3/ C composite, will
0.057mol sodium oxalates, 0.09mol ammonium dihydrogen phosphates, 0.03mol titanium dioxide, 0.03mol manganese dioxide, 1.45g glucose,
1400g zirconium oxide ball milling pearls are added, a certain amount of acetone is added and is used as abrasive media；
Step (2)：The ball milling 12h under rotating speed 800r/min, is placed in 80 DEG C of baking ovens and dries, excessively 100 after crushing grinding~
400 mesh sieves, obtain Na4MnTi(PO4)3/ C composite presoma；
Step (3)：Presoma obtained by step (2) is sintered into 6h under 400 DEG C, high-purity argon gas atmosphere, then heated up 700 DEG C
Sinter 18h, programming rate：5 DEG C/min, Na can be obtained after natural cooling3MnTi(PO4)3/ C composite；
This comparative example resulting materials dephasign is more, and chemical property is poor discharge platform is not obvious.Discharge ratio under 1C multiplying powers
Capacity is 36mAh g-1, after 100 circle circulations, discharge capacity still maintains 16mAh g-1。
Comparative example 2
Raw material sintering schedule is set to 400 DEG C of sintering.
Step (1)：The present embodiment design generation 0.03mol target products Na3MnTi(PO4)3/ C composite, will
0.045mol sodium oxalates, 0.09mol ammonium dihydrogen phosphates, 0.03mol titanium dioxide, 0.03mol manganese dioxide, 1.45g glucose,
1400g zirconium oxide ball milling pearls are added, a certain amount of acetone is added and is used as abrasive media；
Step (2)：The ball milling 12h under rotating speed 800r/min, is placed in 80 DEG C of baking ovens and dries, excessively 100 after crushing grinding~
400 mesh sieves, obtain Na4MnTi(PO4)3/ C composite presoma；
Step (3)：Presoma obtained by step (2) is sintered into 24h, programming rate under 400 DEG C, high-purity argon gas atmosphere：5
DEG C/min, Na can be obtained after natural cooling3MnTi(PO4)3/ C composite；
This comparative example resulting materials dephasign is more, substantially without electro-chemical activity in operating voltage interval.
Claims (10)
1. a kind of Na3MnTi(PO4)3/ C composite, it is characterised in that：By carbon coating Na3MnTi(PO4)3Particle is constituted.
2. Na according to claim 13MnTi(PO4)3/ C composite, it is characterised in that：Na3MnTi(PO4)3Particle
Footpath is 100~2000nm, 5~50nm of carbon coating layer thickness.Na3MnTi(PO4)3With trigonal system, space group is
3. the Na described in claim 1 or 23MnTi(PO4)3The preparation method of/C composite, it is characterised in that：By sodium source, phosphorus
After source, titanium source, manganese source and carbon source ball milling mixing, it is placed in protective atmosphere, is first warming up to 300~400 DEG C of sintering, then be warming up to
500~900 DEG C of sintering, are produced.
4. Na according to claim 33MnTi(PO4)3The preparation method of/C composite, it is characterised in that：Sodium source, phosphorus
The consumption in source, titanium source and manganese source presses Na:P:Ti:Mn mol ratio is 2.6~3.4:3:0.8~1.2:0.8~1.2 metering；
The consumption of the carbon source is the Na of generation3MnTi(PO4)3The 5%~300% of/C composite quality.
5. Na according to claim 43MnTi(PO4)3The preparation method of/C composite, it is characterised in that：The sodium source
Including sodium carbonate, sodium acid carbonate, sodium acetate, sodium oxalate, sodium nitrate, sodium sulphate, niter cake, sodium citrate, sodium hydroxide, nitre
At least one of sour sodium, sodium oxalate；
Phosphorus source includes at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, disodium hydrogen phosphate, sodium dihydrogen phosphate；
The titanium source includes at least one of titanium dioxide, titanyl sulfate, titanium sulfate；
The manganese source is included in manganese monoxide, manganese dioxide, mangano-manganic oxide, manganese sulfate, protochloride manganese, manganese oxalate, manganese nitrate
It is at least one；
The carbon source includes glucose, starch, citric acid, ascorbic acid, polyvinyl alcohol, polyethylene glycol oxide, poly-dopamine, poly- third
At least one of alkene nitrile, poly-dopamine, polyvinylpyrrolidone, CNT, carbon fiber, graphene.
6. the Na according to any one of claim 3~53MnTi(PO4)3The preparation method of/C composite, its feature exists
In：The condition of the ball milling is：Ball material mass ratio is 30~100:1；Engine speed is 300~1600r/min, and Ball-milling Time is
6~48h.
7. Na according to claim 63MnTi(PO4)3The preparation method of/C composite, it is characterised in that：Described ball
Mill is carried out in organic solvent medium.
8. the Na according to claim 3~5,7 any one3MnTi(PO4)3The preparation method of/C composite, its feature exists
In：After sodium source, phosphorus source, titanium source, manganese source and carbon source ball milling mixing, dried at a temperature of being placed in 80~120 DEG C, cross 100~400 mesh
Sieve, takes minus sieve powder to be sintered.
9. the Na according to claim 3~5,7 any one3MnTi(PO4)3The preparation method of/C composite, its feature exists
In：It is 0~12h in the time of 300~400 DEG C of sintering, is 6~24h in the time of 500~900 DEG C of sintering, heating rate is 2
~10 DEG C/min.
10. the Na described in claim 1 or 23MnTi(PO4)3The application of/C composite, it is characterised in that：As sodium ion just
Pole materials application.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710330646.XA CN106981641B (en) | 2017-05-11 | 2017-05-11 | Carbon-coated titanium manganese sodium phosphate composite material, preparation method thereof and application thereof in sodium-ion battery |
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| CN201710330646.XA CN106981641B (en) | 2017-05-11 | 2017-05-11 | Carbon-coated titanium manganese sodium phosphate composite material, preparation method thereof and application thereof in sodium-ion battery |
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| CN106981641A true CN106981641A (en) | 2017-07-25 |
| CN106981641B CN106981641B (en) | 2020-05-05 |
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| CN107978738A (en) * | 2017-11-13 | 2018-05-01 | 中南大学 | A kind of composite positive pole of manganese pyrophosphate sodium/carbon and its preparation and application |
| CN107978739A (en) * | 2017-11-15 | 2018-05-01 | 中南大学 | A kind of fluorinated phosphate manganese titanium sodium/carbon composite and preparation method thereof and the application as sodium ion positive electrode |
| CN108598394A (en) * | 2018-03-30 | 2018-09-28 | 武汉理工大学 | Carbon coating titanium phosphate manganese sodium micron ball and its preparation method and application |
| CN108832099A (en) * | 2018-06-15 | 2018-11-16 | 中南大学 | A kind of richness sodium phase sodium-ion battery positive material and its preparation and application |
| CN108963235A (en) * | 2018-08-01 | 2018-12-07 | 武汉理工大学 | Graphene enhances carbon coating titanium phosphate manganese sodium micron ball electrode material and its preparation method and application |
| CN110311098A (en) * | 2018-03-25 | 2019-10-08 | 北京金羽新能科技有限公司 | A kind of carbon coating titanium phosphate sodium composite material and its sodium-ion battery of preparation |
| CN110611080A (en) * | 2018-06-15 | 2019-12-24 | 中南大学 | Transition metal doped titanium manganese phosphate sodium/carbon composite positive electrode material, preparation thereof and application thereof in sodium ion battery |
| CN110611079A (en) * | 2018-06-15 | 2019-12-24 | 中南大学 | Titanium-manganese bimetallic sodium phosphate @ carbon composite material, preparation thereof and application thereof in sodium-ion battery |
| CN110957490A (en) * | 2019-07-30 | 2020-04-03 | 哈尔滨工业大学 | Preparation method of carbon-coated sodium iron phosphate electrode material with hollow structure |
| CN111186861A (en) * | 2020-01-09 | 2020-05-22 | 南京大学 | Layered chromium-based positive electrode material of sodium ion battery and preparation method thereof |
| CN111342022A (en) * | 2020-03-12 | 2020-06-26 | 东莞理工学院 | Carbon-coated Na3MnTi(PO4)3/C composite material electrode and preparation method and application thereof |
| CN111916741A (en) * | 2020-07-09 | 2020-11-10 | 江苏理工学院 | Preparation method and application of sodium titanium phosphate/carbon composite material |
| CN112786857A (en) * | 2021-01-19 | 2021-05-11 | 华南师范大学 | Fast ion conductor sodium secondary battery positive electrode material and preparation method and application thereof |
| CN113764662A (en) * | 2021-07-29 | 2021-12-07 | 武汉理工大学 | Carbon-coated vanadium-titanium-manganese-sodium phosphate micro-spheres and preparation method and application thereof |
| CN113929069A (en) * | 2021-10-08 | 2022-01-14 | 中国科学院过程工程研究所 | Manganese-rich phosphate cathode material and preparation method and application thereof |
| CN114156452A (en) * | 2021-11-30 | 2022-03-08 | 上海瑞浦青创新能源有限公司 | Sodium ion positive electrode material and preparation method and application thereof |
| CN114373922A (en) * | 2022-01-07 | 2022-04-19 | 北京理工大学 | Manganese-based NASICON type sodium ion positive electrode material and preparation method and application thereof |
| CN116477593A (en) * | 2022-01-15 | 2023-07-25 | 太仓中科赛诺新能源科技有限公司 | High-stability high-conductivity composite titanium phosphorus oxide and preparation method thereof |
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| CN113929069A (en) * | 2021-10-08 | 2022-01-14 | 中国科学院过程工程研究所 | Manganese-rich phosphate cathode material and preparation method and application thereof |
| CN113929069B (en) * | 2021-10-08 | 2023-09-22 | 中国科学院过程工程研究所 | Manganese-rich phosphate positive electrode material and preparation method and application thereof |
| CN114156452A (en) * | 2021-11-30 | 2022-03-08 | 上海瑞浦青创新能源有限公司 | Sodium ion positive electrode material and preparation method and application thereof |
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| CN116477593A (en) * | 2022-01-15 | 2023-07-25 | 太仓中科赛诺新能源科技有限公司 | High-stability high-conductivity composite titanium phosphorus oxide and preparation method thereof |
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