CN107978738A - A kind of composite positive pole of manganese pyrophosphate sodium/carbon and its preparation and application - Google Patents
A kind of composite positive pole of manganese pyrophosphate sodium/carbon and its preparation and application Download PDFInfo
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Abstract
The invention belongs to sodium-ion battery positive material field, specifically discloses a kind of composite positive pole of manganese pyrophosphate sodium/carbon, is the mixing material of manganese pyrophosphate sodium and carbon, the chemical formula of the manganese pyrophosphate sodium is Na6.24Mn4.88(P2O7)4.The invention also discloses the preparation method and application of the composite positive pole.Na of the present invention6.24Mn4.88(P2O7)4High voltage platform with more than 3.8V, and its three-dimensional channel structure opened is conducive to the distortion of lattice of diffusion and the reduction of sodium ion, and the multiplying power and cycle performance of material are excellent.Preparation method of the present invention is simple, and repeatability is high, of low cost, has great commercial application prospect.
Description
Technical field
The present invention relates to sodium-ion battery positive material field, and in particular to a kind of manganese pyrophosphate sodium composite positive pole and
Its preparation method.
Background technology
Lithium ion battery is due to advantages such as high-energy-density, high stability, long-lives, having occupied rapidly portable
Electronic product (laptop, intelligent mobile equipment, tablet computer etc.) market, and constantly oozed to electric vehicle field
Enter.But lithium resource reserves in the earth's crust are low, and Regional Distribution is uneven so that lithium ion battery is promoted and applied on a large scale
During lithium valency it is constantly soaring, cause lithium ion battery to hold at high price.Therefore, lithium ion battery is led in extensive storing up electricity
The application in domain is difficult to really realize.Sodium-ion battery is since sodium resource reserves enrich, environmental-friendly, it is considered to be a kind of preferable
Extensive storing up electricity application technology and obtain the extensive concern in the world.
In past tens year, researcher has carried out the positive electrode of sodium-ion battery widely studied.
In existing positive electrode system, polyanionic chemical combination objects system be considered as the sodium-ion battery of most commercial promise just
Pole material system.In polyanionic chemical combination objects system, pyrophosphate system material is due to logical with open ion diffusion
Road, and material structure stability and heat endurance are high, cause world's extensive concern.Na2MnP2O7With than Na2FeP2O7Higher
Voltage and theoretical energy density, it is considered to be a kind of positive electrode of great application prospect.However, due to Na2MnP2O7It is intrinsic
Electronic conductivity is relatively low and ion diffusion energy barrier is higher, therefore its theoretical specific capacity is also difficult under very low discharge current
To reach, and its cycle performance and high rate performance are also very poor.
The content of the invention
Existing in the prior art to solve the problems, such as, an object of the present disclosure is, there is provided a kind of manganese pyrophosphate sodium/carbon is answered
Close positive electrode, it is desirable to provide one kind has high voltage, the composite positive pole of high circulation stability.
Another object of the present invention is to provide it is a kind of it is reproducible, be simple to operate and friendly to environment, of low cost, have
The preparation method of the sodium-ion battery composite positive pole of prospects for commercial application.
Another object of the present invention is to obtained material is used for sodium-ion battery.
A kind of composite positive pole of manganese pyrophosphate sodium/carbon (also abbreviation composite positive pole of the invention), is manganese pyrophosphate
The mixing material of sodium and carbon, the chemical formula of the manganese pyrophosphate sodium is Na6.24Mn4.88(P2O7)4.With existing manganese base sodium ion
Cell positive material is compared, Na of the present invention6.24Mn4.88(P2O7)4High voltage platform with more than 3.8V, and it is opened
The three-dimensional channel structure put is conducive to the diffusion of sodium ion and reduces the distortion of lattice triggered by jahn teller effect,
The multiplying power and cycle performance of material are obviously improved.
The manganese pyrophosphate sodium of chemical formula of the present invention is the manganese pyrophosphate sodium of non-stoichiometric.
Composite positive pole of the present invention, its sodium element, manganese element, the molar ratio of P elements are 6.24: 4.88: 8.
Na of the present invention6.24Mn4.88(P2O7)4Crystal form be anorthic system, space group P-1.
Composite positive pole of the present invention, is the mixing material of carbon and manganese pyrophosphate sodium, is, for example, carbon and pyrophosphoric acid
The homogeneous mixture of manganese sodium, or the manganese pyrophosphate sodium of the chemical formula are compounded in the surface of carbon.
In the composite positive pole, the content of carbon is 3~30wt%.
The carbon is one kind or more in conductive black, acetylene black, carbon nanotubes, graphene and redox graphene
Kind.
Present invention also offers a kind of preparation method of the composite positive pole of the manganese pyrophosphate sodium/carbon, by described
Na, Mn of chemical formula, P element ratio sodium source, manganese source, phosphorus source are mixed, then under an inert atmosphere the in 250~450 DEG C
Once calcine, obtain intermediate product；After intermediate product is mixed with carbon material again under an inert atmosphere second in 500~600 DEG C
Secondary calcining, obtains the composite positive pole.
Under the ratio, using the method for two steps calcining, pre-sintering first obtains the presoma (intermediate product) of material,
Presoma on the one hand can be reduced into the particle diameter of material by mixing (such as ball milling) with carbon material, while improve carbon material and work
The contact of property material, and carbon material prevent to some extent the serious agglomeration problem of subsequent calcination process in which materials.
The sodium source is preferably that can in aqueous dissolve and ionizable discharge Na+Compound.
Preferably, the sodium source is in sodium carbonate, sodium acid carbonate, sodium acetate, sodium dihydrogen phosphate and disodium hydrogen phosphate
One or more.
The manganese source is preferably that can in aqueous dissolve and ionizable discharge Mn2+Compound.
Preferably, the manganese source is manganese dioxide, the one or more in manganese acetate, manganese oxalate, manganese oxide.
Preferably, phosphorus source is ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, disodium hydrogen phosphate and biphosphate
One or more in sodium.
In the present invention, the sodium source of the ratio, manganese source, phosphorus source material are preferably preferably passed through into ball milling mixing；Mechanical milling process
In can add ball milling solvent, such as ethanol；The rotating speed of ball milling is, for example, 400~500rpm；Ball-milling Time is, for example, 6~10h.
Material after ball milling is subjected to first time calcining under inert atmosphere (protective atmosphere).
Calcined under the first time calcining heat, obtained intermediate product is more advantageous to after being mixed with carbon material
Second follow-up of calcining, is more advantageous to obtaining thing phase purity height, crystallinity height, electric property, it is more excellent to be particularly cycle performance
Composite positive pole.
Preferably, the calcining heat of calcining is 300~350 DEG C for the first time.
Preferably, the inert atmosphere for argon gas, nitrogen and it is hydrogen-argon-mixed in one or more.
Under the material proportion and calcining heat, preferable first time calcination time is 2~9h；Further preferably
For 3~4h.
In the present invention, first time calcined product (intermediate product) and carbon material are mixed, the mode of mixing is preferably
High-energy ball milling.
Intermediate product and carbon material preferably ball milling under an inert atmosphere；The rotating speed of ball milling is, for example, 450~550rpm；Ball milling
Time is, for example, 1~2h.
Preferably, the carbon material is conductive black, acetylene black, carbon nanotubes, graphene and reduction-oxidation graphite
One or more in alkene.
The carbon material dosage is the 3~30% of obtained product quality (theoretical product quality), be that is to say, described
Carbon material, added by the 3~30% of the weight of the composite positive pole.
Second of calcining is calcined under the inert atmosphere similar with calcining for the first time.
The temperature control of second of calcining is in the scope, and the crystallinity of material is more preferable, the electricity of obtained material
Performance is more excellent.
Preferably, second of calcining heat is 500~550 DEG C.
Coordinate the temperature of calcining and second of calcining for the first time, the time of preferable second of calcining is 4~12h；Into
One step is preferably 8~12h.
The preferred preparation method of composite positive pole of the present invention, by phosphorus source, sodium source, manganese source stoichiometrically ball
Mill mixing, 2~9h is then calcined in 250~450 DEG C for the first time under an inert atmosphere, obtains intermediate product；Then in indifferent gas
Intermediate product and carbon material are mixed into 0.5~3.5h by high-energy ball milling under atmosphere, then under an inert atmosphere in 500~600 DEG C
4~12h of secondary clacining, obtains product Na6.24Mn4.88(P2O7)4/ C composite.
Present invention also offers a kind of application of the composite positive pole of the manganese pyrophosphate sodium/carbon, lives as cathode
Property material, is used to prepare sodium-ion battery cathode.
For example, by the Na6.24Mn4.88(P2O7)4After/C composite is mixed with conductive agent and binding agent, pass through coating
On aluminium foil, sodium-ion battery cathode is made.Used conductive agent, binding agent can use well-known to those skilled in the art
Material.The method that assembling prepares sodium-ion battery positive material also refers to existing method.
For example, the obtained Na of the present invention6.24Mn4.88(P2O7)4/ C composite is with conductive black and PVDF binding agents according to 8: 1
: 1 mass ratio is ground, and NMP is added after being sufficiently mixed and forms uniform slurry, coated in electric as test on aluminium foil
Pole, using metallic sodium as to electrode, its electrolyte is 1M NaClO4/ 100%PC, prepares sodium half-cell and tests its electrochemistry
Energy.
Present invention additionally comprises the sodium-ion battery being assembled into using the cathode, the method for assembling can use existing routine
Method.
Present invention additionally comprises the spherical vanadium phosphate manganese sodium composite positive pole of the carbon coating is used to prepare sodium-ion battery
Cathode, and test its chemical property.
Beneficial effects of the present invention：
The present invention proposes a kind of Na6.24Mn4.88(P2O7)4/ C composite positive poles, the high voltage with more than 3.8V are put down
Platform, and stable structure.The material is used for sodium-ion battery, shows good high rate performance and cycle performance, significant increase
The chemical property of manganese base polyanionic positive electrode.For example, capacity is up to 80mAh g under the multiplying power of 2C-1More than；
Under the multiplying power of 0.5C, the capacity retention ratio of the circle of circulation 100 may be up to 91.3%.
Preparation method of the present invention, it is simple and reliable, it is environmental-friendly, of low cost, there is preferable industrial applications prospect
Preparation method.
Brief description of the drawings
【Fig. 1】For Na made from embodiment 16.24Mn4.88(P2O7)4The scanning electron microscope (SEM) photograph (SEM) of/C composite positive poles；
【Fig. 2】For Na made from embodiment 16.24Mn4.88(P2O7)4The XRD diagram of/C composite positive poles；
【Fig. 3】Na is made for embodiment 16.24Mn4.88(P2O7)4The multiplying power of the sodium-ion battery of/C composite positive poles assembling
Performance map；
【Fig. 4】Na is made for embodiment 16.24Mn4.88(P2O7)4The 0.5C of the sodium-ion battery of/C composite positive poles assembling
The cycle performance figure of multiplying power
Embodiment
Following embodiments 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
Take 1.653g (0.0156mol) sodium carbonate, 5.980g (0.0244mol) manganese acetates and 5.282g (0.04mol) phosphorus
Sour hydrogen diammonium pours into 68ml absolute ethyl alcohols in ball grinder, ball milling 8h under the rotating speed of 450rpm, after drying under an argon atmosphere
350 DEG C of calcining 3h, obtain intermediate product.By the acetylene black of intermediate product and theoretical product quality 10wt% argon gas atmosphere ball
High-energy ball milling (rotating speed 500rpm) 1.5h in grinding jar, then lower 550 DEG C of argon gas atmosphere calcines 8h again, obtains product Na6.24Mn4.88
(P2O7)4/ C composite.
Obtained Na6.24Mn4.88(P2O7)4The pattern (SEM) of/C composite is shown in Fig. 1.Using manufactured in the present embodiment
Sodium-ion battery composite positive pole is assembled into button cell with sodium piece, and the material high rate performance is superior as can be seen from Figure 3, i.e.,
Make still there are 74.8mAh g under the multiplying power of 2C-1Capacity.From Fig. 4 circulation it can be seen from the figure thats, circulated under 0.5C
Its specific discharge capacity reaches 87.2mAh/g after 100 circles, and capacity retention ratio is up to more than 90%.
Embodiment 2
Take 1.653g (0.0156mol) sodium carbonate, 5.980g (0.0244mol) manganese acetates and 5.282g (0.04mol) phosphorus
Sour hydrogen diammonium pours into 68ml absolute ethyl alcohols in ball grinder, ball milling 8h under the rotating speed of 450rpm, after drying under an argon atmosphere
350 DEG C of calcining 3h, obtain intermediate product.By the acetylene black of intermediate product and theoretical product quality 10wt% argon gas atmosphere ball
High-energy ball milling (500rpm) 1.5h in grinding jar, then lower 500 DEG C of argon gas atmosphere calcines 8h again, obtains product Na6.24Mn4.88
(P2O7)4/ C composite.
Button cell is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece, 0.5C's
Under multiplying power, specific capacity is 82mAh/g after the circle of circulation 100, and it is 85.2% that capacity retention ratio, which reaches,.Still have under the multiplying power of 2C
71.4mAh g-1Illustrate that calcining heat have impact on the crystallinity of material, and then influence the chemical property of material.
Embodiment 3
Take 1.653g (0.0156mol) sodium carbonate, 5.980g (0.0244mol) manganese acetates and 5.282g (0.04mol) phosphorus
Sour hydrogen diammonium pours into 68ml absolute ethyl alcohols in ball grinder, ball milling 8h under the rotating speed of 450rpm, after drying under an argon atmosphere
350 DEG C of calcining 3h, obtain intermediate product.By the acetylene black of intermediate product and theoretical product quality 5wt% argon gas atmosphere ball
High-energy ball milling (500rpm) 1.5h in grinding jar, then lower 600 DEG C of argon gas atmosphere calcines 8h again, obtains product Na6.24Mn4.88
(P2O7)4/ C composite.Button cell is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece
Under the multiplying power of 0.5C, specific capacity is 83.4mAh/g after the circle of circulation 100, and it is 84.7% that capacity retention ratio, which reaches,.Under the multiplying power of 2C still
So there is 70.1mAhg-1。
Embodiment 4
Take 1.653g (0.0156mol) sodium carbonate, 5.980g (0.0244mol) manganese acetates and 5.282g (0.04mol) phosphorus
Sour hydrogen diammonium pours into 68ml absolute ethyl alcohols in ball grinder, ball milling 8h under the rotating speed of 450rpm, after drying under an argon atmosphere
350 DEG C of calcining 3h, obtain intermediate product.By the acetylene black of intermediate product and theoretical product quality 10wt% argon gas atmosphere ball
High-energy ball milling (500rpm) 1.5h in grinding jar, then lower 550 DEG C of argon gas atmosphere calcines 12h again, obtains product Na6.24Mn4.88
(P2O7)4/ C composite.
Button cell, times of 0.5C are assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece
Under rate, specific capacity is 84.5mAh/g after the circle of circulation 100, and it is 85.1% that capacity retention ratio, which reaches,.Still have under the multiplying power of 2C
72.3mAh g-1。
Embodiment 5
Take 2.621g (0.0312mol) sodium acid carbonate, 5.980g (0.0244mol) manganese acetates and 5.282g (0.04mol)
Diammonium hydrogen phosphate pours into 68ml absolute ethyl alcohols in ball grinder, ball milling 8h under the rotating speed of 450rpm, in argon gas atmosphere after drying
Lower 300 DEG C of calcinings 4h, obtains intermediate product.By the conductive black of intermediate product and theoretical product quality 10wt% in argon gas atmosphere
Ball grinder in high-energy ball milling (500rpm) 1.5h, then again argon gas atmosphere it is lower 550 DEG C calcining 8h, obtain product Na6.24Mn4.88
(P2O7)4/ C composite.Button electricity is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece
Pond, under the multiplying power of 0.5C, specific capacity be 85.7mAh/g after the circle of circulation 100, and capacity retention ratio is reached for 85.6%.Under the multiplying power of 2C
Still there is 73.3mAhg-1。
Embodiment 6
Take 2.621g (0.0312mol) sodium acid carbonate, 2.121g (0.0244mol) manganese dioxide and 5.282g
(0.04mol) diammonium hydrogen phosphate pours into 50ml absolute ethyl alcohols in ball grinder, ball milling 8h under the rotating speed of 450rpm, after dry
300 DEG C of calcining 4h under an argon atmosphere, obtain intermediate product.By intermediate product and the conductive black of theoretical product quality 20wt%
High-energy ball milling (500rpm) 1.5h in the ball grinder of argon gas atmosphere, then lower 550 DEG C of argon gas atmosphere calcines 8h again, obtains product
Na6.24Mn4.88(P2O7)4/ C composite.Assembled using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece
Into button cell, under the multiplying power of 0.5C, specific capacity be 83.1mAh/g after the circle of circulation 100, and capacity retention ratio is reached for 84.4%.2C
Multiplying power under still have 72mAhg-1。
Embodiment 7
Take 1.653g (0.0156mol) sodium carbonate, 5.980g (0.0244mol) manganese acetates and 5.282g (0.04mol) phosphorus
Sour hydrogen diammonium pours into 68ml absolute ethyl alcohols in ball grinder, ball milling 8h under the rotating speed of 450rpm, after drying under an argon atmosphere
350 DEG C of calcining 3h, obtain intermediate product.By the carbon nanotubes of intermediate product and theoretical product quality 15wt% in argon gas atmosphere
High-energy ball milling (500rpm) 1.5h in ball grinder, then lower 500 DEG C of argon gas atmosphere calcines 8h again, obtains product Na6.24Mn4.88
(P2O7)4/ C composite.
Button cell is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece, 0.5C's
Under multiplying power, specific capacity is 86.7mAh/g after the circle of circulation 100, capacity retention ratio 89.4%, is still had under the multiplying power of 2C
76.4mAh g-1.
Embodiment 8
Take 1.653g (0.0156mol) sodium carbonate, 5.980g (0.0244mol) manganese acetates and 5.282g (0.04mol) phosphorus
Sour hydrogen diammonium pours into 68ml absolute ethyl alcohols in ball grinder, ball milling 8h under the rotating speed of 450rpm, after drying under an argon atmosphere
350 DEG C of calcining 3h, obtain intermediate product.By the graphene of intermediate product and theoretical product quality 15wt% argon gas atmosphere ball
High-energy ball milling (500rpm) 1.5h in grinding jar, then lower 500 DEG C of argon gas atmosphere calcines 8h again, obtains product Na6.24Mn4.88
(P2O7)4/ C composite.
Button cell is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece, 0.5C's
Under multiplying power, specific capacity is 90.2mAh/g after the circle of circulation 100, capacity retention ratio 91.3%, is still had under the multiplying power of 2C
80.2mAh g-1.
Comparative example 1
This comparative example is inquired into, and under relatively low first time calcining heat, the performance of obtained material is influenced：
Take 1.653g (0.0156mol) sodium carbonate, 5.980g (0.0244mol) manganese acetates and 5.282g (0.04mol) phosphorus
Sour hydrogen diammonium pours into 68ml absolute ethyl alcohols in ball grinder, ball milling 8h under the rotating speed of 450rpm, after drying under an argon atmosphere
150 DEG C of calcining 3h, obtain intermediate product.By the acetylene black of intermediate product and theoretical product quality 10wt% argon gas atmosphere ball
High-energy ball milling (500rpm) 1.5h in grinding jar, then lower 550 DEG C of argon gas atmosphere calcines 8h again, obtains product Na6.24Mn4.88
(P2O7)4/ C composite.Button cell is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece
Under the multiplying power of 0.5C, specific capacity is 53.4mAh/g after the circle of circulation 100, and it is 64.2% that capacity retention ratio, which reaches,.Hold under the multiplying power of 2C
Amount only has 43.6mAh g-1。
Comparative example 2
This comparative example is inquired into, and under second higher of calcining heat, the performance of obtained material is influenced：
Take 1.653g (0.0156mol) sodium carbonate, 5.980g (0.0244mol) manganese acetates and 5.282g (0.04mol) phosphorus
Sour hydrogen diammonium pours into 68ml absolute ethyl alcohols in ball grinder, ball milling 8h under the rotating speed of 450rpm, after drying under an argon atmosphere
350 DEG C of calcining 3h, obtain intermediate product.By the acetylene black of intermediate product and theoretical product quality 10wt% argon gas atmosphere ball
High-energy ball milling (500rpm) 1.5h in grinding jar, then lower 700 DEG C of argon gas atmosphere calcines 8h again, obtains product X RD crystalline phases confusion, miscellaneous
Matter is more.Times of the button cell in 0.5C is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece
It is basic without storage sodium performance under rate.
Comparative example 3
This comparative example is inquired into, and is only once calcined the performance influence on obtained material：
Take 1.653g (0.0156mol) sodium carbonate, 5.980g (0.0244mol) manganese acetates and 5.282g (0.04mol) phosphorus
The acetylene black of sour hydrogen diammonium and theoretical product quality 10wt% pours into 68ml absolute ethyl alcohols in ball grinder, 450rpm's
Ball milling 8h under rotating speed, it is dry after 550 DEG C of calcining 8h under an argon atmosphere, obtain product Na6.24Mn4.88(P2O7)4/ C composite.
Button cell is assembled under the multiplying power of 0.5C using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece, is followed
Specific capacity is 36.7mAh/g after ring 100 encloses, and it is 44.5% that capacity retention ratio, which reaches,.The material prepared is said using once sintered technique
Reunite serious, chemical property is poor.Capacity only has 26.8mAh g under the multiplying power of 2C-1。
Claims (10)
- A kind of 1. composite positive pole of manganese pyrophosphate sodium/carbon, it is characterised in that：For the mixing material of manganese pyrophosphate sodium and carbon, The chemical formula of the manganese pyrophosphate sodium is Na6.24Mn4.88(P2O7)4。
- 2. the composite positive pole of manganese pyrophosphate sodium/carbon as claimed in claim 1, it is characterised in that：The manganese pyrophosphate The crystal form of sodium is anorthic system, space group P-1.
- 3. the composite positive pole of manganese pyrophosphate sodium/carbon as claimed in claim 1 or 2, it is characterised in that：It is described it is compound just In the material of pole, the content of carbon is 3~30wt%.
- 4. a kind of preparation method of the composite positive pole of claims 1 to 3 any one of them manganese pyrophosphate sodium/carbon, it is special Sign is：Sodium source, manganese source, phosphorus source are mixed in Na, Mn of the chemical formula, P element ratio, then under an inert atmosphere Calcined for the first time in 250~450 DEG C, obtain intermediate product；Again under an inert atmosphere 500 after intermediate product is mixed with carbon material Calcined for second in~600 DEG C, obtain the composite positive pole.
- 5. the preparation method of the composite positive pole of manganese pyrophosphate sodium/carbon according to claim 4, it is characterised in that institute Sodium source is stated as the one or more in sodium carbonate, sodium acid carbonate, sodium acetate, sodium dihydrogen phosphate and disodium hydrogen phosphate；The manganese source is manganese dioxide, the one or more in manganese acetate, manganese oxalate, manganese oxide；Phosphorus source is one kind or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate Kind.
- 6. the preparation method of the composite positive pole of manganese pyrophosphate sodium/carbon according to claim 4 or 5, it is characterised in that： The carbon material is the one or more in conductive black, acetylene black, carbon nanotubes, graphene and redox graphene；Carbon material dosage is the 3~30% of composite positive pole quality.
- 7. the preparation method of the composite positive pole of manganese pyrophosphate sodium/carbon according to claim 3, it is characterised in that：The Calcination time is 2~9h；Second of calcination time is 4~12h.
- 8. the preparation method of the composite positive pole of manganese pyrophosphate sodium/carbon according to claim 3, it is characterised in that：Institute The inert atmosphere stated for argon gas, nitrogen and it is hydrogen-argon-mixed in one or more.
- 9. the preparation method of the composite positive pole of manganese pyrophosphate sodium/carbon according to claim 3, it is characterised in that：It is mixed Conjunction mode is ball milling；Intermediate product and carbon material preferably ball milling under an inert atmosphere.
- A kind of 10. application of the composite positive pole of manganese pyrophosphate sodium/carbon described in claim 1 or 2, it is characterised in that：Make For positive electrode active materials, sodium-ion battery cathode is used to prepare.
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