CN109841801A - A kind of carbon coating NaxRyM2(PO4)3Material and its preparation and application - Google Patents
A kind of carbon coating NaxRyM2(PO4)3Material and its preparation and application Download PDFInfo
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Abstract
The present invention relates to a kind of carbon coating NaxRyM2(PO4)3Material and its preparation and application, it is one or more of transition metal element V, Fe, Nb that the R, which adulterates M in NMP,；R is one of doped chemical Li, K, Rb, Cs, Fr, Be, Ca, Mg, Sr, Ba, B, Al, Zn or two kinds or more；0.005≤y < 7, y < x, 1≤x≤7.The carbon coating Na of acquisitionxRyM2(PO4)3The specific capacity of material can be more than theoretical specific capacity, realize the effect of higher energy density.
Description
Technical field
The present invention relates to sodium-ion battery technical field, in particular to a kind of sodium-ion battery positive material.
Technical background
It is well known that due to the features such as Li resource reserve is limited, distribution is concentrated, in necks such as electric vehicle, mobile power supplys
The extensive popularization and application in domain is restricted.It is shown according to related data, by present Li resource consumption rate, global Li money
Source is only capable of maintaining~60 years.The price of carbonic acid Li also has a very great fluctuation process at present, and average price per ton is mentioned from 40,000 in 2015
160,000 yuan of up in Septembers, 2017 are per ton.In this case, need to find suitable resource replace Li in Li ion battery or
Supplement of the person as Li ion battery.In the periodic table of elements, Na and Li are located at same main group, and physicochemical properties are close.On ground
In shell, the reserves of Na are very rich, are 421 times of Li.And Na is widely distributed, cheap.These features replace NA
Li is possibly realized.In addition to this, the advantage for replacing Li with NA further includes No Assets limitation, can scale；Its cathode uses aluminium
Foil rather than copper foil, do not have overdischarge problem；The mature existing production process of lithium ion battery can be continued to use, feasibility is high.Certainly,
Since the radius ratio Li of Na is big, mass ratio Li is heavy, and the Na ion battery of assembling is low compared with Li ion battery energy density.And for
For extensive stored energy application, energy density requirement is not particularly pertinent.Therefore, this, which allows for sodium-ion battery technology, becomes
The new selection of one kind of extensive stored energy application.
The hot spot of sodium-ion battery technical research at present concentrates on positive electrode, negative electrode material, electrolyte and binder four directions
Face.Positive electrode is the key that one of limitation sodium-ion battery capacity.In numerous positive electrodes, phosphoric acid salt positive electrode
(NaxM2 (PO4) 3 (M=TM, such as V4+/V3+, V3+/V2+, Fe3+/Fe2+, Nb5+/Nb4+ and Nb4+/Nb3+ electricity to)) tool
There are Three-dimensional Open ion transport channel (NASICON fast-ionic conductor), higher ion diffusion rates, good structural stability
It is concerned with thermal stability.Due to the tetrahedral inductive effect of PO4, transient metal Mn+oxygen with higher in phosphate
Change reduction potential.NASICON type NaxM2(PO4)3Material is a kind of very promising Na ion battery positive electrode, by
In NASICON type NaxM2(PO4)3Crystal structure is conducive to the diffusion of Na ion, in combination with suitable carbon coating, the multiplying power of material
It has excellent performance.But NaxM2(PO4)3Theoretical specific capacity it is not high, researchers are by the improvement and innovation of preparation method, so that material
Expect nanosizing, effectively increases effective specific capacity of material, under lower multiplying power, the specific capacity of the sodium-ion battery assembled
Close to theoretical specific capacity, still, the theoretical specific capacity of the material be not it is very high, energy density is up to 400Wh/kg (voltage
Platform is up to 3.4V), limit its application field.In order to improve its application potential, Na is improvedxM2(PO4)3The reason of material
It is necessary by specific capacity.
Summary of the invention
To solve the above-mentioned problems, that is, the effective specific capacity of carbon coating NMP material, the particular technique side that the present invention uses are improved
Case is as follows:
A kind of carbon coating NaxRyM2(PO4)3Material, R adulterate M in NMP be one of transition metal element V, Fe, Nb or
It is two or more；R is one of doped chemical Li, K, Rb, Cs, Fr, Be, Ca, Mg, Sr, Ba, B, Al, Zn or two kinds or more；
0.005≤y < 7, y < x, 1≤x≤7；Y is preferably 0.05,0.1,0.5,0.7.
It is prepared by solid-phase ball milling, wetting phase ball milling, sol-gel method or hydro-thermal method；
What preparation process used:
The source M is in the oxide of the transition metal element containing M, hydroxide, carbonate, acetate, oxalates, citrate
One or more；
The source Na is one or more of sodium hydroxide, sodium carbonate, sodium acetate, sodium oxalate, sodium citrate；
The source R is one or both of oxide containing R, hydroxide, carbonate, acetate, oxalates, citrate
More than；
Phosphate is one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, potassium phosphate and sodium phosphate or two kinds or more.
It is prepared using sol-gel method:
It 1) is that x:y:2:3 weighs sodium source, the source R, the source M and phosphate by Na, R, M and P molar ratio；
2) if M valence state is higher than R doping Na in the source MxRyM2(PO4)3It, need to be by the source M and appropriate reducing agent in compound when M valence state
Mixing, and solvent a dissolution is added, heating stirring is at homogeneous mixture solotion at a temperature of 50-90 DEG C；The dosage of reducing agent be with etc.
The source M is reduced to R doping Na completely just in itxRyM2(PO4)3The stoichiometric ratio of middle M valence state is added；
If the source M is that R adulterates NaxRyM2(PO4)3Middle M valence state is directly added into solvent a dissolution and is made mixed it is not necessary that reducing agent is added
Close solution；
3) the load weighted sodium source of step 1), the source R, phosphate and carbon source are added in step 2) solution, stirring forms molten
Glue A；
4) by Sol A be 60-80 DEG C in true temp at rotate 0.5-2h, form gel B, preferable temperature is 70 DEG C, excellent
The choosing revolving time is 1h；
5) gel B is dried in vacuo at 100-150 DEG C 5-20h, forms electrode material presoma C, preferable temperature 120
DEG C, preferably drying time is 12h；
6) by presoma C in an inert atmosphere through being pre-sintered 2-6h, 600-900 DEG C of high temperature sinterings under the conditions of 200-400 DEG C
4-20h adulterates Na to get carbon coating RxRyM2(PO4)3Material；It is preferred that pre-sintering temperature and time are respectively 350 DEG C and 5h；It is preferred that
The high temperature sintering time is 750 DEG C and 8h.
Reducing agent in the step 2) is oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butanal, citric acid, sucrose, apple
One or more of acid, ethanedioic acid, adipic acid；
The solvent a is one of water, ethyl alcohol, ethylene glycol or two kinds or more；Solute and solvent quality ratio are 1:(10
~20)；It is preferably in a proportion of 1:15；
Carbon source described in the step 3) is oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butanal, citric acid, sucrose, apple
One or more of tartaric acid, ethanedioic acid, adipic acid；Carbon source quality is the source Na, the source R, the source M, phosphate and the total matter of carbon source
The 10-30% of amount；It is preferably in a proportion of 20%.
It is prepared using solid-phase ball milling method:
It 1) is that x:y:2:3 weighs sodium source, the source R, the source M and phosphate by Na, R, M and P molar ratio；
2) if M valence state is higher than R doping Na in the source MxRyM2(PO4)3In material when M valence state, the source M need to be mixed with reducing agent；
The dosage of reducing agent is to be equal to it and the source M is reduced to R doping Na completely justxRyM2(PO4)3The chemistry meter of M valence state in material
Amount is than being added；
If the source M is that R adulterates NaxRyM2(PO4)3M valence state in material, it is not necessary that reducing agent is added；
3) by step 1) and 2), load weighted sodium source, the source R, phosphate, reducing agent and carbon source are mixed, and are put into high-energy ball milling
In tank, and quartz ball is added；Quartz ball gross mass and sodium source, the source R, phosphate, reducing agent and carbon source total mass ratio are 1-3:1-2
It is added；Preferred mass ratio is 1:1；
4) mixture in step 3) is placed on ball milling on high energy ball mill, rotational speed of ball-mill 300r/min-600r/min,
Ball-milling Time is 5h-48h；It is preferred that revolving speed is 480r/min, preferably Ball-milling Time is 12h；Before mixture after ball milling is
Drive body A；
5) by precursor A in an inert atmosphere through being pre-sintered 2-6h, 600-900 DEG C of high temperature sinterings under the conditions of 200-400 DEG C
4-20h is to get high capacity NaxRyM2(PO4)3；It is preferred that pre-sintering temperature and time are respectively 350 DEG C and 5h；It is preferred that high temperature sintering
Time is 750 DEG C and 8h.
Reducing agent in the step 2) is oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butanal, citric acid, sucrose, apple
One or more of acid, ethanedioic acid, adipic acid；
Carbon source described in the step 3) is oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butanal, citric acid, sucrose, apple
One or more of tartaric acid, ethanedioic acid, adipic acid；Carbon source quality is the source Na, the source R, the source M, phosphate and the total matter of carbon source
The 10-30% of amount；It is preferably in a proportion of 20%.
It is prepared using wetting phase ball-milling method:
It 1) is that x:y:2:3 weighs sodium source, the source R, the source M and phosphate by Na, R, M and P molar ratio；
2) if M valence state is higher than R doping Na in the source MxRyM2(PO4)3In material when M valence state, the source M need to be mixed with reducing agent；
The dosage of reducing agent is to be equal to it and the source M is reduced to R doping Na completely justxRyM2(PO4)3The chemistry meter of M valence state in material
Amount is than being added；
If the source M is that R adulterates NaxRyM2(PO4)3M valence state in material, it is not necessary that reducing agent is added；3) it is weighed by step 1) and 2)
Good sodium source, the source R, phosphate, reducing agent and carbon source mixing, and appropriate solvent a is added and forms mixed solution b；
4) above-mentioned mixed solution b is put into high-energy ball milling tank, and appropriate quartz ball is added；Quartz ball is according to the total matter of bead
Amount is 1-3:1-2 addition with sodium source, the source R, phosphate, reducing agent and carbon source total mass ratio, and preferred mass ratio is 1:1；
5) ball grinder in step 4) is placed on ball milling on high energy ball mill, rotational speed of ball-mill 300r/min-600r/min,
Ball-milling Time is 5h-48h；It is preferred that revolving speed is 480r/min, preferably Ball-milling Time is 12h；Before mixture after ball milling is
Drive body A；
6) by precursor A in an inert atmosphere through being pre-sintered 2-6h, 600-900 DEG C of high temperature sinterings under the conditions of 200-400 DEG C
4-20h adulterates Na to get carbon coating RxRyM2(PO4)3Material；It is preferred that pre-sintering temperature and time are respectively 350 DEG C and 5h；It is preferred that
The high temperature sintering time is 750 DEG C and 8h；
Reducing agent in the step 2) is oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butanal, citric acid, sucrose, apple
One or more of acid, ethanedioic acid, adipic acid；
Carbon source described in the step 3) is oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butanal, citric acid, sucrose, apple
One or more of tartaric acid, ethanedioic acid, adipic acid；Carbon source quality is the source Na, the source R, the source M, phosphate and the total matter of carbon source
The 10-30% of amount；It is preferably in a proportion of 20%；
Solvent a described in the step 3) is one of water, ethyl alcohol, ethylene glycol or two kinds or more；Sodium source, the source R, phosphorus
Hydrochlorate, reducing agent, carbon source gross mass and solvent a mass ratio are 1:(5~20).It is preferably in a proportion of 1:10.
It is prepared using hydro-thermal method:
It 1) is that x:y:2:3 weighs sodium source, the source R, the source M and phosphate by Na, R, M and P molar ratio；
2) if M valence state is higher than R doping Na in the source MxRyM2(PO4)3In material when M valence state, the source M need to be mixed with reducing agent；
The dosage of reducing agent is to be equal to it and the source M is reduced to R doping Na completely justxRyM2(PO4)3The chemistry meter of M valence state in material
Amount is than being added；
If the source M is that R adulterates NaxRyM2(PO4)3M valence state in material, it is not necessary that reducing agent is added；3) it is weighed by step 1) and 2)
Sodium source well, the source R, phosphate, reducing agent mixing, and appropriate solvent a is added and forms mixed solution b；
4) above-mentioned mixed solution b being put into vacuum reaction kettle and carries out solvent thermal reaction, reaction temperature is 120-240 DEG C,
Reaction time is that 5h-10d. preferable reaction temperature is 200 DEG C；Preferred reaction time is for 24 hours；
5) mixture after reaction is placed in a vacuum drying oven drying and forms precursor A, drying temperature 100-
180 DEG C, drying time 8-24h；It is preferred that drying temperature is 120 DEG C, preferably drying time is 12h；
6) carbon source is weighed, carbon source quality is the 10-30% of precursor A quality, by carbon source and precursor A mixed grinding 1-
10h forms precursor B；It is preferred that carbon source quality is the 20% of forerunner's weight, preferably milling time is 4h；
7) by precursor B in an inert atmosphere through being pre-sintered 2-6h, 600-900 DEG C of high temperature sinterings under the conditions of 200-400 DEG C
4-20h adulterates Na to get carbon coating RxRyM2(PO4)3Material.It is preferred that pre-sintering temperature and time are respectively 350 DEG C and 5h；It is preferred that
The high temperature sintering time is 750 DEG C and 8h；
Reducing agent in the step 2) is oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butanal, citric acid, sucrose, apple
One or more of acid, ethanedioic acid, adipic acid；
Carbon source described in step 6) is oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butanal, citric acid, sucrose, apple
One or more of acid, ethanedioic acid, adipic acid；
Solvent a described in the step 3) is one of water, ethyl alcohol, ethylene glycol or two kinds or more；Sodium source, the source R, phosphorus
Hydrochlorate, reducing agent gross mass and solvent a mass ratio are 1:(5~20)；It is preferably in a proportion of 1:10.
Inert atmosphere described in the step 5 is nitrogen and/or argon gas.
The carbon coating R adulterates NaxRyM2(PO4)3Application of the material as positive electrode in sodium-ion battery.
Beneficial effects of the present invention
NASICON structural compounds have hexagoinal lattice, space group R3c, each MO6 octahedron and 6 PO4 tetrahedrons
It is connected and constitutes NASICON skeleton.Wherein, alkali metal ion Na+ can occupy two different positions: hexa-coordinate A1 (6b) and eight matches
Position A2 (18e).In NASICON type NaxM2(PO4)3(NMP) in two kinds of sites in crystal structure, on eight-coordinate A2 (18e)
Na is known as in Na2 (the referred to as site M2), very active in charge and discharge process, and sodium ion deintercalation occurs, and contributes battery capacity；And six match
Na on position A1 (6b) is known as Na1 (the referred to as site M1), and since the site M1 is inertia site, Na does not occur in charge and discharge process
Ion deinsertion.Limit the specific capacity of NMP.Due to only having the Na in the site M2 that deintercalation occurs, also it is on the site M1 in 1Mol
1 Na deintercalation does not occur, therefore the theoretical specific capacity for resulting in NMP needs to be further improved.
The energy environment that appropriate element R doping changes around the site Na is carried out in the site Na the invention proposes a kind of, into
And realize the deintercalation of M1 Post section Na, the method to improve carbon coating NMP materials theory specific capacity.Thus the carbon that method obtains
Cladding R doping NMP material is as positive electrode for significantly improving sodium-ion battery energy density in sodium-ion battery.
Detailed description of the invention
Fig. 1 is the refine XRD diagram of embodiment 1-4；
Fig. 2 is the charging and discharging curve and high rate performance comparison diagram of embodiment 1-4 and comparative example.
Specific embodiment
Embodiment 1:(sol-gel method prepares carbon coating Na2.9Li0.1V2(PO4)3)
The quality of sodium hydroxide, lithium hydroxide, ammonium metavanadate, ammonium dihydrogen phosphate is weighed for 2.9:0.1:2:3 in molar ratio,
For reducing agent and carbon source select citric acid, by ammonium metavanadate, citric acid, (40.46% makees 1:1 in citric acid in molar ratio first
Carbon source is used as reducing agent, 59.54%) and the mixing of 250ml deionized water, it stirs and is configured to mix through water-bath heating (80 DEG C)
Uniform blue solution is closed, load weighted sodium hydroxide, lithium hydroxide and ammonium dihydrogen phosphate are added in above-mentioned blue solution, stirred
It mixes to form colloidal sol.Again under vacuum conditions by colloidal sol, it is rotated 1 hour through 75 DEG C, forms gel.Then, gel is placed in 130 DEG C
Vacuum oven in dry 10h, form Na2.9Li0.1V2(PO4)3Presoma.Presoma is under inert gas conditions first through 350
DEG C it is pre-sintered 5h, then is the final product carbon coating of the site Na element doping through 750 DEG C of high temperature sintering 8h, after cooling
Na2.9Li0.1V2(PO4)3。
Embodiment 2:(solid-phase ball milling method prepares carbon coating Na2.5Li0.5V2(PO4)3)
The quality of sodium hydroxide, lithium hydroxide, ammonium metavanadate, ammonium dihydrogen phosphate is weighed for 2.5:0.5:2:3 in molar ratio,
Reducing agent and carbon source select citric acid (molar ratio of ammonium metavanadate and citric acid be 1:1, wherein in citric acid 40.46% for also
Former agent, 59.54% is carbon source), above-mentioned substance is mixed and is put into high-energy ball milling tank, and quartz ball is added；Quartz ball gross mass
It is 1:1 addition with sodium hydroxide, lithium hydroxide, ammonium metavanadate, ammonium dihydrogen phosphate and citric acid total mass ratio；It is subsequently placed at high energy
Ball milling on ball mill, rotational speed of ball-mill 480r/min, Ball-milling Time are for 24 hours；Mixture after ball milling is placed in inert atmosphere
Through 350 DEG C of pre-sintering 5h, through 750 DEG C after, 8h is sintered at high temperature into mutually to get carbon coating Na2.5Li0.5V2(PO4)3Material.
Embodiment 3:(wetting phase ball-milling method prepares carbon coating Na2.9K0.1V2(PO4)3)
The quality of sodium hydroxide, potassium hydroxide, ammonium metavanadate, ammonium dihydrogen phosphate is weighed for 2.9:0.1:2:3 in molar ratio,
Reducing agent and carbon source are selected as citric acid, and (molar ratio of ammonium metavanadate and citric acid is 1:1, wherein 40.46% is in citric acid
Reducing agent, 59.54% is carbon source), by said mixture be added high-energy ball milling tank in, and be added 250ml deionized water formed it is mixed
Close solution.Above-mentioned mixed liquor is then placed in ball milling on high energy ball mill, rotational speed of ball-mill 480r/min, Ball-milling Time is for 24 hours；
Mixture after ball milling is taken out, dry 12h forms forerunner to remove the deionized water in mixed liquor in 100 DEG C of drying boxes
Precursor A is then placed in inert atmosphere through 350 DEG C of pre-sintering 5h by body A, and through 750 DEG C after, 8h is sintered at high temperature into phase, i.e.,
Obtain carbon coating Na2.9K0.1V2(PO4)3Material.
Embodiment 4:(hydro-thermal method prepares carbon coating Na2.5K0.5V2(PO4)3)
The quality for weighing sodium hydroxide, potassium hydroxide, vanadium phosphate, ammonium dihydrogen phosphate for 2.5:0.5:2:3 in molar ratio, puts
Enter in vacuum reaction kettle, while 250ml deionized water is added and carries out solvent thermal reaction, reaction temperature is 200 DEG C, and the reaction time is
24h；Mixed liquor after reaction under high pressure is put into drying box, and dry 12h, forms precursor A at a temperature of 100 DEG C；It weighs suitable
Citric acid is measured as carbon source (citric acid quality is the 20% of precursor A quality), precursor A and citric acid are mixed into mortar
Middle grinding 4h forms precursor B；Precursor B is placed in argon atmosphere first through 350 DEG C of pre-sintering 5h, then is burnt through 750 DEG C of high temperature
8h is tied, is carbon coating Na after cooling2.5K0.5V2(PO4)3。
Comparative example: (sol-gel method prepares carbon coating Na3V2(PO4)3)
The quality of sodium hydroxide, ammonium metavanadate, ammonium dihydrogen phosphate is weighed for 3:2:3 in molar ratio, reducing agent and carbon source are equal
For selecting citric acid, first by ammonium metavanadate, citric acid in molar ratio 1:1 (in citric acid 40.46% be used as reducing agent,
59.54% is used as carbon source) and the mixing of 250ml deionized water, it stirs and is configured to through water-bath heating (80 DEG C) uniformly mixed
Load weighted sodium hydroxide and ammonium dihydrogen phosphate are added in above-mentioned blue solution blue solution, and stirring forms colloidal sol.It again will be molten
Glue under vacuum conditions, rotates 1 hour through 75 DEG C, forms gel.Then, gel is placed in 130 DEG C of vacuum oven and is done
Dry 10h forms Na3V2(PO4)3Presoma.Presoma is under inert gas conditions first through 350 DEG C of pre-sintering 5h, then through 750 DEG C
High temperature sintering 8h is carbon coating Na after cooling3V2(PO4)3。
Implementation result:
By in Na3V2(PO4)3The middle site Na carries out appropriate element, as Li and K doping after, change around the site Na
Energy environment improve Na so that deintercalation has occurred in the Na in the part site M13V2(PO4)3Specific capacity, realize Na3V2
(PO4)3Effect beyond theoretical specific capacity.Energy density is improved, and is expected to popularize in more applications.
As seen from Figure 1, after embodiment 1,2,3 and 4 carries out appropriate Li and K doping, not synthesized by circulation method preparation
Na2.9Li0.1V2(PO4)3, Na2.5Li0.5V2(PO4)3, Na2.9K0.1V2(PO4)3And Na2.5K0.5V2(PO4)3It is able to maintain Na3V2
(PO4)3Cell configuration.Illustrate that suitable element doping will not destroy Na3V2(PO4)3Cell configuration.Table 1 is that ICP test obtains
The Na obtained2.9Li0.1V2(PO4)3And Na2.5Li0.5V2(PO4)3The Mass Distribution of middle each element, table 2 are that ICP test obtains
Na2.9K0.1V2(PO4)3And Na2.5K0.5V2(PO4)3The Mass Distribution of middle each element.It can be seen from Tables 1 and 2
Na2.9Li0.1V2(PO4)3, Na2.5Li0.5V2(PO4)3, Na2.9K0.1V2(PO4)3And Na2.5K0.5V2(PO4)3The quality of middle each element
It is close with design flow, show that Li and K enter Na according to design proportion doping3V2(PO4)3In.
Table 3 is that Li is doped into Na3V2(PO4)3The combination energy being calculated behind the middle site Na1 and the site Na2, as the result is shown
Li is doped into that combine behind the site Na1 or Na2 can be lower, shows that Li is easy to be entrained in the site Na, is entrained in the site Na1 compared to Li,
Li is easier to be doped in the site Na2.
Table 1
Table 2
Table 3
It is Na from Fig. 22.9Li0.1V2(PO4)3, Na2.5Li0.5V2(PO4)3, Na2.9K0.1V2(PO4)3、Na2.5K0.5V2(PO4)3
And Na3V2(PO4)3Charging and discharging curve and high rate performance.It as seen from the figure, is 0.5C in multiplying power after Li and K doping
When, battery capacity is more than theoretical specific capacity 117.6mAh g-1 (128.9mAh g-1 (Na2.9Li0.1V2(PO4)3),
141.8mAh g-1(Na2.5Li0.5V2(PO4)3), 119.5mAh g-1 (Na2.9K0.1V2(PO4)3)、129.5mAh g-1
(Na2.5K0.5V2(PO4)3)@0.5C).This is because Na3V2(PO4)3After the middle site Na carries out appropriate element doping, change
Energy environment around the site Na is shown so that deintercalation occurs together for the Na in the site Na and M2 in the part site M1 beyond reason
By the effect of specific capacity.
Claims (10)
1. a kind of carbon coating NaxRyM2(PO4)3Material, it is characterised in that: it is in transition metal element V, Fe, Nb that R, which adulterates M in NMP,
One or more；R is one of doped chemical Li, K, Rb, Cs, Fr, Be, Ca, Mg, Sr, Ba, B, Al, Zn or two
Kind or more；0.005≤y < 7, y < x, 1≤x≤7；Y is preferably 0.05,0.1,0.5,0.7.
2. a kind of carbon coating R described in claim 1 adulterates NaxRyM2(PO4)3The preparation method of material, it is characterised in that: pass through
Solid-phase ball milling, wetting phase ball milling, sol-gel method or hydro-thermal method are prepared；
What preparation process used:
The source M is one in the oxide of the transition metal element containing M, hydroxide, carbonate, acetate, oxalates, citrate
Kind is two or more；
The source Na is one or more of sodium hydroxide, sodium carbonate, sodium acetate, sodium oxalate, sodium citrate；
The source R be one or both of oxide containing R, hydroxide, carbonate, acetate, oxalates, citrate with
On；
Phosphate is one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, potassium phosphate and sodium phosphate or two kinds or more.
3. preparation method according to claim 2, it is characterised in that: be prepared using sol-gel method:
It 1) is that x:y:2:3 weighs sodium source, the source R, the source M and phosphate by Na, R, M and P molar ratio；
2) if M valence state is higher than R doping Na in the source MxRyM2(PO4)3In compound when M valence state, the source M and appropriate reducing agent need to be mixed
It closes, and solvent a dissolution is added, heating stirring is at homogeneous mixture solotion at a temperature of 50-90 DEG C；The dosage of reducing agent is to be equal to
The source M is reduced to R doping Na just by it completelyxRyM2(PO4)3The stoichiometric ratio of middle M valence state is added；
If the source M is that R adulterates NaxRyM2(PO4)3It is molten to be directly added into the obtained mixing of solvent a dissolution it is not necessary that reducing agent is added for middle M valence state
Liquid；
3) the load weighted sodium source of step 1), the source R, phosphate and carbon source are added in step 2) solution, stirring forms Sol A；
4) by Sol A be 60-80 DEG C in true temp at rotate 0.5-2h, form gel B, preferable temperature is 70 DEG C, is preferably revolved
The steaming time is 1h；
5) gel B being dried in vacuo at 100-150 DEG C 5-20h, forms electrode material presoma C, preferable temperature is 120 DEG C,
It is preferred that drying time is 12h；
6) by presoma C in an inert atmosphere through being pre-sintered 2-6h, 600-900 DEG C of high temperature sintering 4- under the conditions of 200-400 DEG C
20h adulterates Na to get carbon coating RxRyM2(PO4)3Material；It is preferred that pre-sintering temperature and time are respectively 350 DEG C and 5h；It is preferred that high
Warm sintering time is 750 DEG C and 8h.
4. preparation method according to claim 3, it is characterised in that: reducing agent in the step 2) is oxalic acid, anti-bad
One or more of hematic acid, formaldehyde, acetaldehyde, n-butanal, citric acid, sucrose, malic acid, ethanedioic acid, adipic acid；
The solvent a is one of water, ethyl alcohol, ethylene glycol or two kinds or more；Solute and solvent quality ratio be 1:(10~
20)；It is preferably in a proportion of 1:15；
Carbon source described in the step 3) is oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butanal, citric acid, sucrose, apple
One or more of acid, ethanedioic acid, adipic acid；Carbon source quality is the source Na, the source R, the source M, phosphate and carbon source gross mass
10-30%；It is preferably in a proportion of 20%.
5. preparation method according to claim 2, it is characterised in that: be prepared using solid-phase ball milling method:
It 1) is that x:y:2:3 weighs sodium source, the source R, the source M and phosphate by Na, R, M and P molar ratio；
2) if M valence state is higher than R doping Na in the source MxRyM2(PO4)3In material when M valence state, the source M need to be mixed with reducing agent；Reduction
The dosage of agent is to be equal to it and the source M is reduced to R doping Na completely justxRyM2(PO4)3The stoichiometric ratio of M valence state in material
It is added；
If the source M is that R adulterates NaxRyM2(PO4)3M valence state in material, it is not necessary that reducing agent is added；
3) by step 1) and 2), load weighted sodium source, the source R, phosphate, reducing agent and carbon source are mixed, and are put into high-energy ball milling tank
In, and quartz ball is added；Quartz ball gross mass adds with sodium source, the source R, phosphate, reducing agent and carbon source total mass ratio for 1-3:1-2
Enter；Preferred mass ratio is 1:1；
4) mixture in step 3) is placed on ball milling on high energy ball mill, rotational speed of ball-mill 300r/min-600r/min, ball milling
Time is 5h-48h；It is preferred that revolving speed is 480r/min, preferably Ball-milling Time is 12h；Mixture after ball milling is presoma
A；
5) by precursor A in an inert atmosphere through being pre-sintered 2-6h, 600-900 DEG C of high temperature sintering 4- under the conditions of 200-400 DEG C
20h is to get high capacity NaxRyM2(PO4)3；It is preferred that pre-sintering temperature and time are respectively 350 DEG C and 5h；It is preferred that when high temperature sintering
Between be 750 DEG C and 8h.
6. preparation method according to claim 5, it is characterised in that: reducing agent in the step 2) is oxalic acid, anti-bad
One or more of hematic acid, formaldehyde, acetaldehyde, n-butanal, citric acid, sucrose, malic acid, ethanedioic acid, adipic acid；
Carbon source described in the step 3) is oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butanal, citric acid, sucrose, apple
One or more of acid, ethanedioic acid, adipic acid；Carbon source quality is the source Na, the source R, the source M, phosphate and carbon source gross mass
10-30%；It is preferably in a proportion of 20%.
7. preparation method according to claim 2, it is characterised in that: be prepared using wetting phase ball-milling method:
It 1) is that x:y:2:3 weighs sodium source, the source R, the source M and phosphate by Na, R, M and P molar ratio；
2) if M valence state is higher than R doping Na in the source MxRyM2(PO4)3In material when M valence state, the source M need to be mixed with reducing agent；Reduction
The dosage of agent is to be equal to it and the source M is reduced to R doping Na completely justxRyM2(PO4)3The stoichiometric ratio of M valence state in material
It is added；
If the source M is that R adulterates NaxRyM2(PO4)3M valence state in material, it is not necessary that reducing agent is added；3) by step 1) and 2) load weighted
Sodium source, the source R, phosphate, reducing agent and carbon source mixing, and appropriate solvent a is added and forms mixed solution b；
4) above-mentioned mixed solution b is put into high-energy ball milling tank, and appropriate quartz ball is added；Quartz ball according to bead gross mass with
Sodium source, the source R, phosphate, reducing agent and carbon source total mass ratio are 1-3:1-2 addition, and preferred mass ratio is 1:1；
5) ball grinder in step 4) is placed on ball milling on high energy ball mill, rotational speed of ball-mill 300r/min-600r/min, ball milling
Time is 5h-48h；It is preferred that revolving speed is 480r/min, preferably Ball-milling Time is 12h；Mixture after ball milling is presoma
A；
6) by precursor A in an inert atmosphere through being pre-sintered 2-6h, 600-900 DEG C of high temperature sintering 4- under the conditions of 200-400 DEG C
20h adulterates Na to get carbon coating RxRyM2(PO4)3Material；It is preferred that pre-sintering temperature and time are respectively 350 DEG C and 5h；It is preferred that high
Warm sintering time is 750 DEG C and 8h；
Reducing agent in the step 2) be oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butanal, citric acid, sucrose, malic acid,
One or more of ethanedioic acid, adipic acid；
Carbon source described in the step 3) is oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butanal, citric acid, sucrose, apple
One or more of acid, ethanedioic acid, adipic acid；Carbon source quality is the source Na, the source R, the source M, phosphate and carbon source gross mass
10-30%；It is preferably in a proportion of 20%；
Solvent a described in the step 3) is one of water, ethyl alcohol, ethylene glycol or two kinds or more；Sodium source, the source R, phosphoric acid
Salt, reducing agent, carbon source gross mass and solvent a mass ratio are 1:(5~20).It is preferably in a proportion of 1:10.
8. preparation method according to claim 2, it is characterised in that: be prepared using hydro-thermal method:
It 1) is that x:y:2:3 weighs sodium source, the source R, the source M and phosphate by Na, R, M and P molar ratio；
2) if M valence state is higher than R doping Na in the source MxRyM2(PO4)3In material when M valence state, the source M need to be mixed with reducing agent；Reduction
The dosage of agent is to be equal to it and the source M is reduced to R doping Na completely justxRyM2(PO4)3The stoichiometric ratio of M valence state in material
It is added；
If the source M is that R adulterates NaxRyM2(PO4)3M valence state in material, it is not necessary that reducing agent is added；3) by step 1) and 2) load weighted
Sodium source, the source R, phosphate, reducing agent mixing, and appropriate solvent a is added and forms mixed solution b；
4) above-mentioned mixed solution b is put into vacuum reaction kettle and carries out solvent thermal reaction, reaction temperature is 120-240 DEG C, reaction
Time is that 5h-10d. preferable reaction temperature is 200 DEG C；Preferred reaction time is for 24 hours；
5) mixture after reaction is placed in a vacuum drying oven drying and forms precursor A, drying temperature 100-180
DEG C, drying time 8-24h；It is preferred that drying temperature is 120 DEG C, preferably drying time is 12h；
6) carbon source is weighed, carbon source quality is the 10-30% of precursor A quality, by carbon source and precursor A mixed grinding 1-10h, shape
At precursor B；It is preferred that carbon source quality is the 20% of forerunner's weight, preferably milling time is 4h；
7) by precursor B in an inert atmosphere through being pre-sintered 2-6h, 600-900 DEG C of high temperature sintering 4- under the conditions of 200-400 DEG C
20h adulterates Na to get carbon coating RxRyM2(PO4)3Material.It is preferred that pre-sintering temperature and time are respectively 350 DEG C and 5h；It is preferred that high
Warm sintering time is 750 DEG C and 8h；
Reducing agent in the step 2) be oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butanal, citric acid, sucrose, malic acid,
One or more of ethanedioic acid, adipic acid；
Carbon source described in step 6) is oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butanal, citric acid, sucrose, malic acid, second
One or more of diacid, adipic acid；
Solvent a described in the step 3) is one of water, ethyl alcohol, ethylene glycol or two kinds or more；Sodium source, the source R, phosphoric acid
Salt, reducing agent gross mass and solvent a mass ratio are 1:(5~20)；It is preferably in a proportion of 1:10.
9. according to preparation method described in claim 3,5,7 or 9, it is characterised in that: inert atmosphere described in the step 5
For nitrogen and/or argon gas.
10. a kind of carbon coating R described in claim 1 adulterates NaxRyM2(PO4)3Material is as positive electrode in sodium-ion battery
In application.
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