CN108511711A - A kind of laminated structure vanadium phosphate sodium composite positive pole and preparation method thereof - Google Patents
A kind of laminated structure vanadium phosphate sodium composite positive pole and preparation method thereof Download PDFInfo
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- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The invention discloses a kind of laminated structure vanadium phosphate sodium composite positive poles and preparation method thereof, belong to electrochemical technology field.A kind of laminated structure vanadium phosphate sodium composite positive pole and preparation method thereof of the present invention, operating procedure is:A certain amount of sodium source, phosphorus source, vanadium source, carbon source are subjected to ball milling in organic solvent, then by dry, high-temperature burning process, you can obtain laminated structure vanadium phosphate sodium composite positive pole.The present invention prepares gained laminated structure vanadium phosphate sodium composite positive pole, and charge/discharge capacity is high, and cycle performance and high rate performance are excellent, and this method is compared with the preparation method of other vanadium phosphate sodium composite positive poles, simple for process, flow is short, securely and reliably, metaplasia production can be amplified.
Description
Technical field
The invention belongs to battery material preparing technical fields, and in particular to arrive a kind of laminated structure vanadium phosphate sodium anode composite
Material and preparation method thereof.
Background technology
With being continuously increased for population in the world, economic fast development, a large amount of consumption of the energy, people are faced with severe
Crisis of resource, meanwhile, the exhaustive exploitation of traditional fossil energy, also along with the appearance of the problem of environmental pollutions such as greenhouse effects, because
This develops a kind of cleaning, pollution-free, reproducible new energy replaces traditional fossil energy and realized energy conversion using it
The problem of through becoming most attention all over the world.Electro-chemical conversion technology due to can the effectively optimizing energy distribution, realize the energy
Efficient utilization, and be widely studied.Wherein, lithium rechargeable battery is the most successful technology of exploitation, big with energy density,
Operating voltage is high, has extended cycle life, many advantages, such as environmental pollution is small, still, content of the lithium resource in the earth's crust it is less and
It is unevenly distributed, is on the high side, to constrain lithium ion battery by large-scale promotion application.
For lithium, rich reserves of the sodium resource in the earth's crust and widely distributed are cheap, it is most important that, sodium
Element and elemental lithium are located at same main group, have similar physico-chemical property and memory mechanism, therefore have very much can for sodium-ion battery
Lithium ion battery can be substituted, the much-talked-about topic of novel power battery research is become.Na with NASICON type frame structures3V2
(PO4)3(NVP) compared with other sodium-ion battery positive materials, there is high ion conductivity, high platform voltage (~3.4V), height
The advantages that energy density (~400Wh/kg) and good structural stability.However, NVP has lower electron conductivity, sternly
Its electric conductivity is affected again and hinders the performance of its height ratio capacity.Most common solution is carbon coating, in high―temperature nuclei
In the process, organosilane precursor cognition high temperature cabonization obtains the good amorphous carbon of electric conductivity, enhances electric conductivity.In addition, in addition to carbon packet
It covers, pattern and microstructure are also most important to the raising of NVP chemical properties.
Through retrieval, the NVP composite positive poles for having some different-shapes at present are prepared out.As application publication number is
The application case of 105336924 A of CN discloses a kind of carbon-coated vanadium phosphate sodium positive electrode, and microstructure is that size is uniform
Particle;105098179 B of Authorization Notice No. CN are prepared for a kind of carbon coating vanadium phosphate of nano bar-shape using method of electrostatic spinning
Sodium positive electrode;105552328 A of application publication number CN, as carbon source, tool have been synthesized by sol-gel method using agarose
There is the carbon coating vanadium phosphate sodium graininess positive electrode of three dimensional skeletal structure.
The chemical property that above-mentioned application case prepares gained NVP composite positive poles has obtained a degree of raising,
The present inventor also has been devoted to the preparation process and performance study of NVP composite positive poles, it is expected that can pass through system
The optimization of standby technique and NVP appearance structures further increases the chemical property of NVP composite positive poles.
Invention content
1. technical problems to be solved by the inivention
It is an object of the invention to overcome the shortcomings of the prior art, and provide a kind of laminated structure carbon coating phosphoric acid
Vanadium sodium composite positive pole and preparation method thereof.Preparation process using the present invention can be prepared with unique laminated structure
Vanadium phosphate sodium composite positive pole, and stacking straggly between vanadium phosphate sodium piece and piece, clear layer is clearly demarcated, to make electrolyte
With open osmotic space, the diffusion length of sodium ion is shortened, the completion of electrochemical reaction is accelerated, effectively improves phosphorus
The chemical property of sour vanadium sodium composite positive pole.
2. technical solution
In order to achieve the above objectives, technical solution provided by the invention is:
A kind of laminated structure vanadium phosphate sodium composite positive pole of the present invention, the vanadium phosphate sodium composite positive pole is by sheet
The stacking formation straggly of vanadium phosphate sodium, vanadium phosphate sodium coated with uniform has carbon-coating, and the thickness of vanadium phosphate sodium thin slice is 10-
30nm。
The preparation method of a kind of laminated structure vanadium phosphate sodium composite positive pole of the present invention, by a certain amount of sodium source, phosphorus
Source, vanadium source and carbon source, which are placed in organic solvent, carries out ball milling, then by dry, high-temperature burning process, you can obtain sheet knot
Structure vanadium phosphate sodium composite positive pole, the carbon source are saccharide compound, and additive amount is the 30-80wt% of vanadium phosphate sodium.
Further, the time of the ball milling is 12-24h, rotating speed 30-90r/min.
Further, the organic solvent is any one in alcohols, ketone or arbitrary combination.
Further, the sodium source is sodium carbonate, sodium oxalate, sodium citrate, sodium phosphate, sodium dihydrogen phosphate, lactic acid
Sodium, sodium fluoride, sodium bicarbonate, sodium chloride, enuatrol, sodium sulphate, sodium lactate, sodium nitrate, sodium hydroxide, sodium alginate, bromination
Sodium, odium stearate, sodium laurate, sodium acetate any one or arbitrary combination.
Further, the phosphorus source is ammonium dihydrogen phosphate, phosphoric acid, sodium dihydrogen phosphate, diammonium hydrogen phosphate, di(2-ethylhexyl)phosphate fourth
Any one in ester, metaphosphoric acid, butylphosphoric acid ester, diphenyl phosphate azide or arbitrary combination.
Further, the vanadium source is ammonium metavanadate, two sodium vanadates, vanadic anhydride, vanadium carbonyl, vanadium peroxide
Acid, sodium metavanadate, vanadic sulfate, positive vanadic acid, vanadium dioxide, dibrominated vanadium, dioxy chlorine vanadium, vanadium dichloride, diiodinating vanadium, difluoro
Change vanadium, vanadium trioxide, vanadium hydroxide, triiodide vanadium, vanadium trifluoride, trifluoro vanadyl, trisulfides three vanadium, vanadium trichloride, trichlorine
Any one in vanadyl, vanadous bromide, vanadium tetrafluoride, vanadium tetrachloride, vanadium pentafluoride, vanadium pentasulfide or arbitrary combination.
Further, the molar ratio of the sodium source, phosphorus source and vanadium source is 3:3:2.
Further, the temperature being dried after ball milling is 60-80 DEG C, time 12-24h.
Further, the calcine technology is divided into two steps, and wherein the temperature of precalcining is 300-500 DEG C, and the time is
3-6h;The temperature of secondary clacining is 600-800 DEG C, time 8-15h.
3. advantageous effect
Using technical solution provided by the invention, compared with prior art, there is following remarkable result:
(1) a kind of laminated structure vanadium phosphate sodium composite positive pole of the invention, the vanadium phosphate sodium composite positive pole by
The stacking formation straggly of sheet vanadium phosphate sodium, vanadium phosphate sodium coated with uniform has carbon-coating, and the thickness of vanadium phosphate sodium thin slice is 10-
30nm, clear layer is clearly demarcated between piece and piece, to effectively improve the contact area of electrolyte and electrode, accelerate electrolyte
Infiltration, shorten the diffusion length of sodium ion, accelerate the diffusion of sodium ion, and then it is compound just to significantly improve vanadium phosphate sodium
The chemical property of pole material.The laminated structure vanadium phosphate sodium composite positive pole
(2) a kind of laminated structure vanadium phosphate sodium composite positive pole of the invention, unique laminated structure make vanadium phosphate
Sodium has larger specific surface area, can buffer volume change of the vanadium phosphate sodium in charge and discharge process, effectively maintain it
The integrality of microscopic appearance, to improve the cycle performance and high rate performance of electrode material.
(3) preparation method of a kind of laminated structure vanadium phosphate sodium composite positive pole of the invention, using solid phase reduction method,
And to the concrete technology of reaction, especially by carbon source and organic solvent preferably and cooperation, to be prepared in the form of sheets
The structure vanadium phosphate sodium straggly for stacking distribution, makes electrolyte have open osmotic space, shortens the diffusion length of sodium ion, add
The speed completion of electrochemical reaction, effectively improves the chemical property of vanadium phosphate sodium.
(4) preparation method of a kind of laminated structure vanadium phosphate sodium composite positive pole of the invention, easy to operate, flow
Shorter, reaction condition is controllable, can industrialized production, in high-performance sodium-ion battery have preferable development prospect.
Description of the drawings
Fig. 1 is the x-ray diffraction pattern of 1 products therefrom of the embodiment of the present invention;
Fig. 2 is the stereoscan photograph of 1 products therefrom of the embodiment of the present invention;
Fig. 3 is the high rate performance figure of 1 products therefrom of the embodiment of the present invention.
Specific implementation mode
The preparation method of a kind of laminated structure vanadium phosphate sodium composite positive pole of the present invention, by a certain amount of sodium source, phosphorus
Source, vanadium source and carbon source, which are placed in organic solvent, carries out ball milling, and wherein the molar ratio of sodium source, phosphorus source and vanadium source is 3:3:2, the carbon
Source is saccharide compound, and additive amount is the 30-80wt% of vanadium phosphate sodium, and the organic solvent is arbitrary in alcohols, ketone
A kind of or arbitrary combination, Ball-milling Time 12-24h, rotating speed 30-90r/min.Then the presoma obtained after ball milling is set
Dry 10-24h, carries out high-temperature burning process again later at 60-90 DEG C, which is divided into two steps, wherein precalcining
Temperature is 300-500 DEG C, time 3-6h;The temperature of secondary clacining is 600-800 DEG C, time 8-15h, you can obtain sheet
Structure vanadium phosphate sodium composite positive pole.It is straggly by sheet vanadium phosphate sodium that the present invention prepares gained vanadium phosphate sodium composite positive pole
It stacks and is formed, vanadium phosphate sodium coated with uniform has carbon-coating, and the thickness of vanadium phosphate sodium thin slice is 10-30nm.
Currently, the research emphasis of existing a large number of researchers is all how to improve the electrochemistry of NVP composite positive poles
Can, and common method mainly carries out carbon coating.In addition, it has been investigated that, the appearance structure of NVP composite positive poles is to it
Chemical property also has large effect, and graininess, rodlike and three-dimensional framework knot have been prepared in currently available technology
The NVP composite positive poles of structure, but it is related open not yet about the vanadium phosphate sodium composite positive pole of laminated structure.The present invention
Inventor also have been devoted to the performance studies of NVP composite positive poles, study through a large number of experiments, finally found that and adopt
With the solid phase reduction method of the present invention, and to specific reaction process, especially by carbon source and organic solvent preferably and cooperation,
To which the vanadium phosphate sodium straggly for stacking distribution of structure in the form of sheets be prepared, make electrolyte that there is open osmotic space, contracting
The short diffusion length of sodium ion, accelerates the completion of electrochemical reaction, and then effectively improve the electrochemistry of vanadium phosphate sodium
Energy.
The method that the application case that application publication number is 106450298 A of CN is combined using hydro-thermal method and solid-phase sintering, system
Standby to have obtained LiFePO4-phosphoric acid vanadium lithium composite positive pole of laminated structure, it is anti-to refer to high pressure in specific operation process
It answers kettle to assist, while needing to be passed through protective atmosphere, precursor powder is obtained by processes such as washing, filtering, drying, grindings,
Then calcining obtains LiFePO4-phosphoric acid vanadium lithium composite positive pole in non-oxidizing atmosphere.But there are following for this application
Disadvantage:1. autoclave is expensive, and short life, consumptive material consumption is more;2. whole operation process flow is tediously long, complicated.Application
Nano flaky lithium iron phosphate and preparation method thereof disclosed in 104201335 A of publication No. CN uses hydro-thermal method synthesis, reference
Expensive surfactant cetyl trimethylammonium bromide (CTAB), meanwhile, it also strictly to be controlled in preparation process
The additive amount of CTAB and vitamin c processed, avoid ferrous ion from being oxidized to iron ion.This application prepares gained nanometer sheet simultaneously
Although first charge-discharge capacity of the shape lithium iron phosphate positive material under C/3 current conditions is higher, under high current density,
Its chemical property need further to improve and reinforce.And the preparation process and easy to operate of the present invention, flow is shorter, instead
Answer condition controllable, can industrialized production, the final chemical property for preparing gained vanadium phosphate sodium composite positive pole had
Effect improves, and has preferable development prospect in high-performance sodium-ion battery.
To further appreciate that present disclosure, in conjunction with specific embodiment, the present invention is described in detail.It needs to illustrate
, sodium source of the invention is sodium carbonate, sodium oxalate, sodium citrate, sodium phosphate, sodium dihydrogen phosphate, sodium lactate, sodium fluoride, carbon
Sour hydrogen sodium, sodium chloride, enuatrol, sodium sulphate, sodium lactate, sodium nitrate, sodium hydroxide, sodium alginate, sodium bromide, odium stearate,
Sodium laurate, sodium acetate any one or arbitrary combination;Phosphorus source is ammonium dihydrogen phosphate, phosphoric acid, sodium dihydrogen phosphate, phosphoric acid hydrogen two
Any one in ammonium, dibutylphosphoric acid ester, metaphosphoric acid, butylphosphoric acid ester, diphenyl phosphate azide or arbitrary combination;Vanadium source is inclined vanadium
Sour ammonium, two sodium vanadates, vanadic anhydride, vanadium carbonyl, vanadium peroxy acid, sodium metavanadate, vanadic sulfate, positive vanadic acid, vanadium dioxide,
Dibrominated vanadium, dioxy chlorine vanadium, vanadium dichloride, diiodinating vanadium, vanadium difluoride, vanadium trioxide, vanadium hydroxide, triiodide vanadium, three
Vanadium fluoride, trifluoro vanadyl, trisulfides three vanadium, vanadium trichloride, vanadium oxytrichloride, vanadous bromide, vanadium tetrafluoride, vanadium tetrachloride, five fluorine
Change any one in vanadium, vanadium pentasulfide or arbitrary combination.Since length is limited, below only list portion in specific embodiment
Division example, and without enumerating.
Embodiment 1
Precise 4.68g sodium dihydrogen phosphates, 1.82g vanadic anhydrides and 1.37g glucose are placed in ball grinder, then
Absolute ethyl alcohol and agate ball are added, for 24 hours with the rotating speed ball milling of 30r/min.After ball milling is complete, suspension is obtained, is subsequently placed in drum
12h is dried in wind drying box at 80 DEG C.Finally, precursor powder is placed in tube furnace, in Ar-H2(95:5) gaseous mixture
In atmosphere, respectively at secondary clacining 12h at precalcining 4h at 350 DEG C and 750 DEG C to get to the laminated structure vanadium phosphate of the present embodiment
Sodium composite positive pole.
Fig. 1 is the X-ray diffractogram that the present embodiment prepares products therefrom, its crystallinity is preferable and all as seen from the figure
Diffraction maximum can index turn to vanadium phosphate sodium.Fig. 2 is the field emission scanning electron microscope photo that the present embodiment prepares products therefrom, shows institute
The NVP/C of preparation is laminated structure, and sheet thickness is in 20nm or so.The present embodiment is prepared into products therefrom and conductive agent, is bonded
Agent is according to 7:2:1 mass ratio is made into slurry, is equably coated on positive plate, and in gloves together with sodium piece, electrolyte, diaphragm
Half-cell is assembled into case, Fig. 3 show the high rate performance curve of the half-cell.As seen from the figure, 1,2,5,10,20,
Under 30 and 50C current densities, specific discharge capacity is respectively 104,101,98,94,86,72 and 64mAh/g, and works as current density
When again returning to 1C, specific discharge capacity remains to reach 102mAh/g, capacity almost without decaying, show good times it is forthright
Energy.
Embodiment 2
Precise 2.46g sodium acetates, 1.5g vanadium trioxides, 2.94g phosphoric acid and 2.88g sucrose are placed in ball grinder,
Then methanol and agate ball are added, with the rotating speed ball milling 12h of 48r/min.After ball milling is complete, suspension is obtained, is subsequently placed in drum
12h is dried in wind drying box at 80 DEG C.Finally, precursor powder is placed in tube furnace, in Ar-H2(95:5) gaseous mixture
In atmosphere, precalcining 4h and 750 DEG C of secondary clacining 12h is compound just to get the laminated structure vanadium phosphate sodium to the present embodiment at 350 DEG C
Pole material, cycle and high rate performance are closer to embodiment 1.
Embodiment 3
Precise 4.68g sodium dihydrogen phosphates, 1.82g vanadic anhydrides and 1.37g maltose are placed in ball grinder, then
Acetone and agate ball are added, with the rotating speed ball milling 18h of 30r/min.After ball milling is complete, suspension is obtained, it is dry to be subsequently placed in air blast
20h is dried in dry case at 80 DEG C.Finally, precursor powder is placed in tube furnace, in Ar-H2(95:5) mixed atmosphere
In, precalcining 4h and 750 DEG C of secondary clacining 12h follows to get to laminated structure vanadium phosphate sodium composite positive pole at 350 DEG C
Ring and high rate performance are closer to embodiment 1.
Embodiment 4
Precise 4.68g sodium dihydrogen phosphates, 2.34g ammonium metavanadates, 2.00g glucose and 1.65g fructose are placed in ball milling
In tank, ethylene glycol and agate ball are then added, with the rotating speed ball milling 14h of 60r/min.After ball milling is complete, suspension is obtained, then
Dry 10h is placed in air dry oven at 90 DEG C.Finally, precursor powder is placed in tube furnace, in Ar-H2(95:5)
In mixed atmosphere, precalcining 6h and 750 DEG C of secondary clacining 12h is to get to laminated structure vanadium phosphate sodium anode composite material at 300 DEG C
Material, cycle and high rate performance are closer to embodiment 1.
Embodiment 5
Precise 1.59g sodium carbonate, 1.82g vanadic anhydrides, 3.45g ammonium dihydrogen phosphates and 1.37g fructose are placed in ball
In grinding jar, espeleton, ethyl alcohol and agate ball are then added, with the rotating speed ball milling 12h of 30r/min.After ball milling is complete, hanged
Turbid is subsequently placed in air dry oven at 80 DEG C dry 16h.Finally, precursor powder is placed in tube furnace, in Ar-
H2(95:5) in mixed atmosphere, precalcining 3h and 600 DEG C of secondary clacining 8h is to get to the sheet knot of the present embodiment at 500 DEG C
Structure vanadium phosphate sodium composite positive pole, sheet thickness are slightly better than embodiment 1 in 10nm or so, cycle and high rate performance.
Embodiment 6
Precise 2.55g sodium nitrate, 1.82g vanadic anhydrides, 3.45g ammonium dihydrogen phosphates, 1.88g sucrose and 1.00g
Maltose is placed in ball grinder, then adds ethylene glycol, methylisobutylketone and agate ball, with the rotating speed ball milling of 90r/min
24h.After ball milling is complete, suspension is obtained, is subsequently placed in air dry oven and is dried for 24 hours at 60 DEG C.Finally, by precursor powder
It is placed in tube furnace, in Ar-H2(95:5) in mixed atmosphere, at 400 DEG C precalcining 4h and 800 DEG C of secondary clacining 15h to get
To laminated structure vanadium phosphate sodium composite positive pole, sheet thickness is slightly worse than in fact in 30nm or so, cycle and high rate performance
Apply example 1.
Claims (10)
1. a kind of laminated structure vanadium phosphate sodium composite positive pole, it is characterised in that:The vanadium phosphate sodium composite positive pole is by piece
The stacking formation straggly of shape vanadium phosphate sodium, vanadium phosphate sodium coated with uniform has carbon-coating, and the thickness of vanadium phosphate sodium thin slice is 10-
30nm。
2. a kind of preparation method of laminated structure vanadium phosphate sodium composite positive pole as described in claim 1, it is characterised in that:
A certain amount of sodium source, phosphorus source, vanadium source and carbon source are placed in organic solvent and carry out ball milling, then by dry, high-temperature calcination
Journey, you can obtain laminated structure vanadium phosphate sodium composite positive pole, the carbon source is saccharide compound, and additive amount is vanadium phosphate
The 30-80wt% of sodium.
3. a kind of preparation method of laminated structure vanadium phosphate sodium composite positive pole according to claim 2, feature exist
In:The time of the ball milling is 12-24h, rotating speed 30-90r/min.
4. a kind of preparation method of laminated structure vanadium phosphate sodium composite positive pole according to claim 2, feature exist
In:The organic solvent is any one or arbitrary combination in alcohols, ketone.
5. a kind of preparation side of laminated structure vanadium phosphate sodium composite positive pole according to any one of claim 2-4
Method, it is characterised in that:The sodium source is sodium carbonate, sodium oxalate, sodium citrate, sodium phosphate, sodium dihydrogen phosphate, sodium lactate, fluorine
Change sodium, sodium bicarbonate, sodium chloride, enuatrol, sodium sulphate, sodium lactate, sodium nitrate, sodium hydroxide, sodium alginate, sodium bromide, hard
Resin acid sodium, sodium laurate, sodium acetate any one or arbitrary combination.
6. a kind of preparation side of laminated structure vanadium phosphate sodium composite positive pole according to any one of claim 2-4
Method, it is characterised in that:The phosphorus source be ammonium dihydrogen phosphate, phosphoric acid, sodium dihydrogen phosphate, diammonium hydrogen phosphate, dibutylphosphoric acid ester, partially
Any one in phosphoric acid, butylphosphoric acid ester, diphenyl phosphate azide or arbitrary combination.
7. a kind of preparation side of laminated structure vanadium phosphate sodium composite positive pole according to any one of claim 2-4
Method, it is characterised in that:The vanadium source is ammonium metavanadate, two sodium vanadates, vanadic anhydride, vanadium carbonyl, vanadium peroxy acid, inclined vanadium
Sour sodium, vanadic sulfate, positive vanadic acid, vanadium dioxide, dibrominated vanadium, dioxy chlorine vanadium, vanadium dichloride, diiodinating vanadium, vanadium difluoride, three
V 2 O, vanadium hydroxide, triiodide vanadium, vanadium trifluoride, trifluoro vanadyl, trisulfides three vanadium, vanadium trichloride, vanadium oxytrichloride, three
Any one in bromination vanadium, vanadium tetrafluoride, vanadium tetrachloride, vanadium pentafluoride, vanadium pentasulfide or arbitrary combination.
8. a kind of preparation side of laminated structure vanadium phosphate sodium composite positive pole according to any one of claim 2-4
Method, it is characterised in that:The molar ratio of the sodium source, phosphorus source and vanadium source is 3:3:2.
9. a kind of preparation side of laminated structure vanadium phosphate sodium composite positive pole according to any one of claim 2-4
Method, it is characterised in that:The temperature being dried after ball milling is 60-80 DEG C, time 12-24h.
10. a kind of preparation side of laminated structure vanadium phosphate sodium composite positive pole according to any one of claim 2-4
Method, it is characterised in that:The calcine technology is divided into two steps, and the wherein temperature of precalcining is 300-500 DEG C, time 3-6h;
The temperature of secondary clacining is 600-800 DEG C, time 8-15h.
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Cited By (4)
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CN110581274A (en) * | 2019-10-09 | 2019-12-17 | 湖南工程学院 | Preparation method of carbon-coated sodium vanadium phosphate |
CN111490239A (en) * | 2020-04-15 | 2020-08-04 | 安徽师范大学 | Vanadium sodium phosphate/nitrogen-doped carbon composite sodium ion battery positive electrode material and preparation method thereof, positive electrode piece and sodium ion battery |
CN113299889A (en) * | 2021-04-27 | 2021-08-24 | 合肥国轩电池材料有限公司 | Lithium battery positive electrode material and preparation method and application thereof |
CN115304046A (en) * | 2022-09-08 | 2022-11-08 | 四川大学 | Sodium vanadium phosphate, sodium vanadium manganese phosphate and preparation method thereof |
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CN115304046A (en) * | 2022-09-08 | 2022-11-08 | 四川大学 | Sodium vanadium phosphate, sodium vanadium manganese phosphate and preparation method thereof |
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