CN107017394A - A kind of pyrophosphoric acid cobalt sodium/carbon graphite alkene anode composite material, preparation and application - Google Patents
A kind of pyrophosphoric acid cobalt sodium/carbon graphite alkene anode composite material, preparation and application Download PDFInfo
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Abstract
The invention discloses a kind of pyrophosphoric acid cobalt sodium/carbon graphite alkene anode composite material and preparation method thereof：By cobalt source, sodium source, phosphorus source is dissolved separately in deionized water according to metering ratio, is added acidic metal complexing reagent regulation pH, is stirring evenly and then adding into a certain amount of graphene solution prepared in above-mentioned solution.It is heated to forming gel in water-bath after well mixed, evaporating water obtains presoma under vacuum drying oven afterwards, is sintered under protective gas after being ground, and obtains a kind of sodium-ion battery anode composite material Na2CoP2O7@C are interspersed on graphene.Preparation method of the present invention is simple, mild condition.Prepared sodium-ion battery positive material epigranular, pattern is good, and the material is used for sodium-ion battery, with height ratio capacity, high voltage, and illustrates good stable circulation performance.
Description
Technical field
The invention belongs to sodium-ion battery field, and in particular to a kind of sodium-ion battery anode composite material and its preparation side
Method.
Background technology
At present, fossil fuel is still main power supply resource.However as the irrational exploitation of the mankind and utilization, fossil
The energy day is becoming tight, and environmental pollution is increasingly serious.Therefore, new cleaning resource and regenerative resource, such as sun are developed
Energy, wind energy, tide energy etc. become the task of top priority.But then, the normal operation of power network needs the generating of steady and continuous, too
Positive energy, wind energy, tide energy etc. are restricted by factors such as weather, place and times, be significantly limit it and on a large scale should
With and popularization.In order to solve the problem, extensive electricity storage technology becomes an important field of research.Wherein, secondary cell
Due to higher energy density and transformation efficiency, becoming the prioritizing selection of extensive storing up electricity, and have extended cycle life and have
The lithium ion battery for having high-energy-density is considered as great promising secondary cell.From 1990s lithium ion
Since battery successfully comes out, it has obtained the application of considerable scale in terms of electric automobile, mancarried electronic aid, but with lithium
The continuous progress and development of ion battery, a series of hidden danger has also gradually been exposed among the visual field of people.The limited money of lithium
Source and constantly soaring cost of material will certainly the seriously extensive development of limiting lithium ion cell and applications.Therefore exploitation one
Plant cheap, sustainable development battery system extremely urgent.
Sodium and lithium are located at same main group, and with similar physics and chemical property, and sodium resource reserve is abundant, can be continuous
From seawater extract.Although for lithium, sodium ion radius is larger, standard electrochemical current potential is relatively low, causes sodium ion
The energy density and power density of battery are relatively low, but following increase and battery size size with the market demand is excellent
Change, with low cost, safe sodium-ion battery has quite wide prospect, the rear lithium epoch will certainly be turned into most important
One of developing direction.
Positive electrode is the key of sodium-ion battery development, but has that voltage platform is low, specific capacity is not high and the life-span owes
Good the problems such as, the positive electrode of exploitation high voltage, height ratio capacity and good stability is particularly critical.Polyanionic Na2CoP2O7
With stable three-dimensional structure, cycle life is excellent and possesses the advantages such as higher discharge platform, but material prepare it is difficult, miscellaneous
Xiang Duo, poorly conductive and pattern are difficult to control to.
The content of the invention
An object of the present disclosure is that (present invention is also labeled as offer pyrophosphoric acid cobalt sodium/carbon graphite alkene anode composite material
Na2CoP2O7/ C/RGO, or be Na2CoP2O7@C@RGO)。
Second purpose of the invention is the preparation method for providing a kind of pyrophosphoric acid cobalt sodium/carbon graphite alkene anode composite material,
Aim to provide a kind of simple, reproducible, with low cost, the environment-friendly preparation method of technique.
3rd purpose of the invention is the application in sodium-ion battery field of the anode composite material described in offer, it is intended to
By described positive electrode, the chemical property of sodium-ion battery is lifted.
A kind of pyrophosphoric acid cobalt sodium/carbon graphite alkene anode composite material, using graphene as substrate, in the three dimensional network of graphene
The composite of pyrophosphoric acid cobalt sodium@carbon is compounded with network.
The anode composite material that the present invention is provided, intersperses positive electrode, institute in the three-dimensional conductive network that graphene is constituted
The positive electrode stated is that (chemical formula is Na to pyrophosphoric acid cobalt sodium2CoP2O7) with the composite (Na of carbon2CoP2O7@C composites).
In the composite of described pyrophosphoric acid cobalt sodium@carbon, carbon material is coated on pyrophosphoric acid cobalt sodium surface.
The inventors discovered that, the anode composite material of described structure and composition, with excellent electric property.
Preferably, described anode composite material particle diameter is 100-900nm.Further preferably, described positive pole is combined
Material particle size is 100-500nm；Still more preferably it is 180~270nm.
Preferably, graphene accounts for anode composite material mass percent for 5-20%；More preferably 10-18%；
Most preferably 10~15%.
Present invention also offers a kind of preparation method of described pyrophosphoric acid cobalt sodium/carbon graphite alkene anode composite material, press
The ratio that Co, Na, P mol ratio are 1: 2: 2 is by cobalt source, sodium source, and phosphorus source, which is dissolved in deionized water, obtains mixed liquor；To mixed liquor
Middle addition acidic metal complexing reagent, adjusts pH, then adds graphene, be heated to forming gel；Gel drying is obtained into forerunner
Body；Presoma is sintered and obtains described anode composite material.
Cobalt source, sodium source, phosphorus source, acidic metal complexing reagent, graphene are first dissolved and/or are dispersed in water by the present invention, are passed through
Cross sol-gal process and presoma is made；Then sinter, obtained anode composite material epigranular, pattern are good, electric conductivity is high.Will
Obtained material can show high charge-discharge specific capacity, good high rate performance and cyclical stability as sodium-ion battery positive pole
Energy.In addition, the inventive method technique is simple, reproducible, with low cost, environment-friendly.
Preparation method of the present invention, in the complexing by the acidic metal complexing reagent and described pH regulation and control,
Pyrophosphoric acid cobalt sodium can be made to be combined with carbon, and latter step is in situ, be evenly distributed in the three-dimensional conductive network of graphene, and nanometer can be made
Level and granularity uniformity is good, the excellent anode composite material of electric property.
A kind of preferred preparation method of the present invention, by cobalt source, sodium source, phosphorus source, acidic metal complexing reagent is according to metering score
It is not dissolved in deionized water, is stirring evenly and then adding into a certain amount of graphene solution prepared in above-mentioned solution.Mixing is equal
Be heated to forming gel in water-bath after even, evaporating water obtains presoma under vacuum drying oven afterwards, after being ground
It is sintered under protective gas, obtains a kind of sodium-ion battery anode composite material Na2CoP2O7@C@RGO。
The anode composite material that the present invention is obtained has higher specific capacity, in addition, by constructing carbon graphite alkene composite junction
Structure, is conducive to the structural stability of material.Be conducive to the raising of its electric conductivity, and then improve its chemical property.
The cobalt source is preferably that can in aqueous dissolve and ionizable discharge Co2+Compound.
Preferably, the cobalt source is at least one of cobalt chloride, cobaltous sulfate, cobalt nitrate, cobalt oxalate, cobalt acetate.
Further preferably, described cobalt source is cobalt chloride, cobalt acetate, one kind of cobalt nitrate.Most preferably cobalt nitrate.
The sodium source is preferably that can in aqueous dissolve and ionizable discharge Na+Compound.
Preferably, described sodium source is sodium carbonate, sodium acid carbonate, sodium acetate, sodium oxalate, sodium nitrate, sodium sulphate, sulfuric acid
At least one of hydrogen sodium.
Further preferably, the sodium source is one kind in sodium carbonate, sodium acid carbonate.
The cobalt source is preferably that can in aqueous dissolve and ionizable discharge PO4 3-Compound.
Preferably, phosphorus source is at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid or pyrophosphoric acid.
Further preferably, described phosphorus source is one kind in diammonium hydrogen phosphate, ammonium dihydrogen phosphate.
Preferably, in the mixed liquor, Co2+Concentration is 0.1-30mol/L；Na+ concentration is 0.2-60mol/L；PO4 3-
Concentration is 0.2-60mol/L.The material particle size prepared in the preferred concentration range is evenly.Excessive concentration, material are reunited existing
As serious, concentration is too low, then material yield is too low.
Further preferably, in the mixed liquor, Co2+Concentration is 0.1-20mol/L；Na+Concentration is 0.2-40mol/L；
PO4 3-Concentration is 0.2-40mol/L.
Still more preferably, in the mixed liquor, Co2+Concentration is 0.5-10mol/L；Na+ concentration is 1-20mol/L；
PO4 3-Concentration is 1-20mol/L.
Preferably, the acidic metal complexing reagent is citric acid, ascorbic acid, tartaric acid, ethylenediamine tetra-acetic acid, poly- third
At least one of olefin(e) acid；More preferably citric acid and/or ascorbic acid.
Preferably, the acidic metal complexing reagent and Co that add2+Mol ratio is 0.5: 1-3: 1.It that is to say, acid metal network
Mixture and the Co in cobalt source mol ratio are 0.5: 1-3: 1.
Acidic metal complexing reagent can preferably promote the complex reaction of metal ion, while can uniformly be coated as carbon source
Material.In the preferred scope, if accounting is too low, pyrophosphoric acid cobalt sodium material surface can not be uniformly coated on；Accounting is too high,
Then carbon content is too high, is unfavorable for the specific capacity of material.
Further preferably, acidic metal complexing reagent and Co2+Mol ratio is 1: 1-2.5: 1, most preferably 1: 1.
Preferably, the pH for adding acidic metal complexing reagent regulation mixed liquor is 2-6.Solution is heated in the range of the pH, energy
Preferably form gel.Further preferably, pH is 4-5.
Preferably, the graphene added and the Na of synthesis2CoP2O7Mass ratio be 0.05-0.2: 1.Stone in the range of being somebody's turn to do
Black alkene dispersiveness preferably, is more uniformly dispersed in solution.
Further preferably, the graphene and Na of addition2CoP2O7Mass ratio be 0.1-0.2: 1
Sintering process is carried out under protective atmosphere.The protective gas is nitrogen and/or argon gas or argon gas/hydrogen
Gas mixed atmosphere.
Preferably, the protective atmosphere is nitrogen atmosphere, argon gas atmosphere, the mixed atmosphere of the hydrogen of 95% argon gas -5%
In one kind.
Preferably, the temperature of sintering process is 600 DEG C -800 DEG C.
In the present invention, subject to the foregoing, then coordinate described sintering temperature, the grain of obtained anode composite material can be made
Degree is uniform, yield is high, impurity is few, tap density is high, good conductivity, can make Na by the inventive method2CoP2O7Material electrochemical
Performance is significantly improved.
Further preferably, sintering temperature is 650-750 DEG C.Most preferably 650-700 DEG C.
The heating rate of sintering process is 1-20 DEG C/min.It is more beneficial for ensureing composite in the preferred heating rate
The regularity of appearance structure.
Further preferably, the heating rate of sintering process is 5-15 DEG C/min.
Under described sintering temperature, sintering time preferably is 2-10h；More preferably 2-6h.
Product after sintering is by washing, dry i.e. obtained described anode composite material.
A kind of preparation method of preferred sodium-ion battery anode composite material of the present invention, comprises the following steps：
Step (a)：In Co, Na, P mol ratio for 1: 2: 2 ratio by cobalt source, sodium source, phosphorus source is soluble in water is arranged to
To Co2+、Na+、PO4 3-Concentration distinguishes 0.5-10mol/L, 1-20mol/L, 1-20mol/L solution；Add afterwards and Co2+Deng
Mole acidic metal complexing reagent；Described acidic metal complexing reagent is citric acid and/or ascorbic acid, adjusts pH to 4-5, most
After add Na2CoP2O710%-20% mass fractions graphene；The mol ratio of acidic metal complexing reagent and the Co in cobalt source
For 0.5: 1-3: 1；
Step (b)：Solution made from step (a) is subjected to heating water bath, is formed to be transferred to after gel in vacuum drying oven and dried
Moisture, obtains presoma and is ground；
Step (c)：Presoma made from step (b) is sintered, sintering temperature is 650-700 DEG C, sintering time is
2-6h, heating rate is 5-15 DEG C/min；Sintered product is scrubbed, be dried to obtain Na2CoP2O7/ C/RGO anode composite materials.
Present invention additionally comprises a kind of using anode composite material made from described preparation method, using graphene as substrate,
The composite of pyrophosphoric acid cobalt sodium@carbon is compounded with the three-dimensional network of graphene.
Na of the present invention2CoP2O7/ C/RGO anode composite materials, are to contain Co2+、Na+、PO4 3-In solution in
Acidic metal complexing reagent is added, graphene solution is added afterwards, heating is evaporated after stirring, and obtains Surface coating carbon graphite
The Na that presoma, the sintering of alkene structure are obtained2CoP2O7/ C/RGO anode composite materials, both ensure that the specific capacity of material, and energy
Solve material conductivity poor, the problem of dephasign is more, pattern is difficult to control to are conducive to improving the cyclical stability of sodium-ion battery.
Preferably, graphene quality accounts for the 5-20% of described anode composite material；More preferably 10-15%.
Present invention also offers a kind of application of described pyrophosphoric acid cobalt sodium/carbon graphite alkene anode composite material, by this just
Pole composite is used as sodium ion positive electrode.
Preferably, described application, is applied to and prepares sodium-ion battery positive pole.Technical scheme is brought
Beneficial effect：
1) Na of the present invention2CoP2O7/ C/RGO anode composite materials have stable three-dimensional structure, cycle life excellent
It is good and possess the advantages such as higher discharge platform, and intersperse positive electrode on good graphene conductive network and greatly carry
Its high electric conductivity, and then lift its chemical property；Research shows that anode composite material of the present invention is close in high current
Degree is lower to have excellent cycle performance.
2) present invention prepares described anode composite material by sol-gal process+Technology for Heating Processing, with traditional solid phase
Method is compared, and the material particle size that the preparation method is obtained is more tiny, is mixed more uniform, is reacted more abundant, the pattern of formation
It is more good, be conducive to avoiding the generation of agglomeration.
3) in preparation method of the present invention, by described cobalt source, sodium source, phosphorus source, acidic metal complexing reagent, graphene with
Na2CoP2O7Weight than regulation and control, can be by carbon content control in suitable scope, and then further lift obtained positive pole
The performance of composite.
4) obtained material of the invention is compared with traditional material, it is ensured that also carried while the chemical property of material
High its cyclical stability and electric conductivity.
5) extensively, operation is simple and reliable for preparation method, reproducible, workable, environment for raw material sources of the invention
It is friendly, with low cost, with certain application prospect.
Brief description of the drawings
【Fig. 1】The scanning electron microscope (SEM) photograph (SEM) of the sodium-ion battery anode composite material made from embodiment 1
【Fig. 2】The discharge cycles curve map of the sodium-ion battery anode composite material made from embodiment 1.
Embodiment
Following examples are intended to be described in further details present invention；And the protection domain of the claims in the present invention
It is not limited by the example.
Embodiment 1
Weigh respectively 0.01mol cobalt nitrates, 0.01mol sodium carbonate and 0.02mol diammonium hydrogen phosphate be dissolved in 50ml go from
In sub- water, 0.01mol citric acids are added afterwards in above-mentioned solution, regulation pH=5 stirs to form homogeneous solution, afterwards by 0.3g
Graphene dispersion, by the aqueous solution as gel is thermally formed in 80 ° of water-baths, is transferred to vacuum afterwards in above-mentioned solution
Presoma is dried to obtain in baking oven.Finally above-mentioned presoma is ground, under an argon atmosphere, 650 DEG C of sintering 3h, programming rate 10
℃/min.Finally product is cleaned, dried.Obtain final products (anode composite material)；.The SEM figures of obtained product
See Fig. 1；Known by Fig. 1, the preferable Na of pattern is finally obtained by sol-gal process+heat treatment2CoP2O7/ C/RGO materials,
Granularity is 180nm.
Anode composite material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 5C current density, chemical property is tested.Fig. 2 is anode composite material putting in current density 5C made from the present embodiment
Electric specific capacity and cycle efficieny data.
From Fig. 2 test results, sodium electricity prepared by this example is just having good chemical property；It is close in 5C electric current
Under degree, specific capacity is reached after 40mAh/g, the circle of circulation 50, remains to keep 32mAh/g specific capacity.It can be kept after the circle of circulation 100
22mAh/g。
Embodiment 2
Weigh respectively 0.01mol cobalt chlorides, 0.01mol sodium oxalates and 0.02mol diammonium hydrogen phosphate be dissolved in 15ml go from
In sub- water, 0.025mol ascorbic acid is added afterwards in above-mentioned solution, regulation pH=2 stirs to form homogeneous solution, afterwards will
0.5g graphene dispersions are in above-mentioned solution.By the aqueous solution as gel is thermally formed in 80 ° of water-baths, it is transferred to afterwards
Presoma is dried to obtain in vacuum drying oven.Finally above-mentioned presoma is ground, under an argon atmosphere, 700 DEG C of sintering 5h, heating speed
Spend 15 DEG C/min.Finally product is cleaned, dried.Obtain final products (anode composite material).Made from the present embodiment
Anode composite material granularity is 270nm.
Anode composite material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 5C current density, chemical property is tested.Under 5C current density, specific capacity is reached after 38mAh/g, the circle of circulation 50,
Remain to keep 30mAh/g specific capacity.21mAh/g can be kept after the circle of circulation 100.
Embodiment 3
Weigh respectively 0.01mol cobalt acetates, 0.02mol sodium acetates and 0.02mol ammonium dihydrogen phosphate be dissolved in 100ml go from
In sub- water, 0.02mol polyacrylic acid is added afterwards in above-mentioned solution, regulation pH=4 stirs to form homogeneous solution, afterwards will
0.5g graphene dispersions are in above-mentioned solution.By the aqueous solution as gel is thermally formed in 80 ° of water-baths, it is transferred to afterwards
Presoma is dried to obtain in vacuum drying oven.Finally above-mentioned presoma is ground, under an argon atmosphere, 800 DEG C of sintering 5h, heating speed
Spend 15 DEG C/min.Finally product is cleaned, dried.Obtain final products (anode composite material).Made from the present embodiment
Anode composite material granularity is 890nm.
Anode composite material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 5C current density, chemical property is tested.Under 5C current density, specific capacity is reached after 35mAh/g, the circle of circulation 50,
Remain to keep 31mAh/g specific capacity.18mAh/g can be kept after the circle of circulation 100.
Embodiment 4
Weigh respectively 0.01mol cobalt chlorides, 0.01mol sodium carbonate and 0.02mol diammonium hydrogen phosphate be dissolved in 80ml go from
In sub- water, 0.01mol tartaric acid is added afterwards in above-mentioned solution, regulation pH=4 stirs to form homogeneous solution, afterwards will
0.15g graphene dispersions are in above-mentioned solution.By the aqueous solution as gel is thermally formed in 80 ° of water-baths, it is transferred to afterwards
Presoma is dried to obtain into vacuum drying oven.Finally above-mentioned presoma is ground, under an argon atmosphere, 700 DEG C of sintering 7h, heating
15 DEG C/min of speed.Finally product is cleaned, dried.Obtain final products (anode composite material).The present embodiment is made
Anode composite material granularity be 270nm.
Anode composite material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 5C current density, chemical property is tested.Under 5C current density, specific capacity is reached after 39mAh/g, the circle of circulation 50,
Remain to keep 30mAh/g specific capacity.18mAh/g can be kept after the circle of circulation 100.
Comparative example 1
Weigh respectively 0.01mol cobalt chlorides, 0.01mol sodium oxalates and 0.02mol diammonium hydrogen phosphate be dissolved in 200ml go from
In sub- water, 0.25mol citric acids are added afterwards in above-mentioned solution, regulation pH=6 stirs to form homogeneous solution, afterwards will
0.01g graphene dispersions are in above-mentioned solution.By the aqueous solution as gel is thermally formed in 80 ° of water-baths, it is transferred to afterwards
Presoma is dried to obtain into vacuum drying oven.Finally above-mentioned presoma is ground, under an argon atmosphere, 650 DEG C of sintering 5h, heating
15 DEG C/min of speed.Finally product is cleaned, dried.Obtain final products (anode composite material).The present embodiment is made
Anode composite material granularity be 370nm.
Anode composite material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 5C current density, chemical property is tested.Under 5C current density, specific capacity is reached after 32mAh/g, the circle of circulation 50,
Only keep 20mAh/g specific capacity.Capacity almost decays to zero after the circle of circulation 100.Seeing as graphene content very little, fail
Good conductive network is preferably formed, causes material property poor.
Comparative example 2
Weigh respectively 0.01mol cobalt nitrates, 0.01mol sodium carbonate and 0.02mol diammonium hydrogen phosphate be dissolved in 50ml go from
In sub- water, stirring forms homogeneous solution, and pH value of solution is 7.6, afterwards by 0.15g graphene dispersions in above-mentioned solution.Will be described
The aqueous solution is heated as in 80 ° of water-baths, is transferred in vacuum drying oven is dried to obtain presoma afterwards.Finally by above-mentioned presoma
Grind, under an argon atmosphere, 700 DEG C of sintering 5h, 15 DEG C/min of programming rate.Finally product is cleaned, dried.Obtain most
Finished product (anode composite material).Anode composite material granularity made from the present embodiment is 370nm.
Anode composite material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 5C current density, chemical property is tested.Under 5C current density, specific capacity reaches 28mAh/g, and voltage platform reaches
After 3V, the circle of circulation 50,20mAh/g specific capacity is only kept.Capacity almost decays to zero after the circle of circulation 100.This material prepared
Material causes material reaction uneven because without acidic metal complexing reagent (such as citric acid) is added, failing to form gel, conductive
Property is too poor, and chemical property is poor.
Comparative example 3
Weigh respectively 0.01mol cobalt chlorides, 0.01mol sodium oxalates and 0.02mol diammonium hydrogen phosphate be dissolved in 15ml go from
In sub- water, 0.02mol tartaric acid is added afterwards in above-mentioned solution, stirring forms homogeneous solution, and 0.3g graphene dispersions are existed
In the aqueous solution, by described 80 DEG C of heating water baths of the aqueous solution, vacuum drying oven drying is transferred to afterwards, is ground.Finally by above-mentioned presoma
Under an argon atmosphere, 1000 DEG C of sintering 8h, 5 DEG C/min of programming rate.Finally product is cleaned, dried.Finally produced
Product (anode composite material)；The sample sintering temperature of this preparation of obtained sample is too high, has exceeded the fusing point of material, sample is not
Powder can be made, it is impossible to test its chemical property.
Comparative example 4
Weigh respectively 0.01mol cobalt nitrates, 0.01mol sodium carbonate and 0.02mol diammonium hydrogen phosphate be dissolved in 50ml go from
In sub- water, 1mol ascorbic acid is added afterwards in above-mentioned solution, regulation pH=1.8 stirs to form homogeneous solution, afterwards will
0.25g graphene dispersions are in above-mentioned solution.By the aqueous solution as gel is thermally formed in 80 ° of water-baths, it is transferred to afterwards
Presoma is dried to obtain into vacuum drying oven.Finally above-mentioned presoma is ground, under an argon atmosphere, 650 DEG C of sintering 6h, heating
12 DEG C/min of speed.Finally product is cleaned, dried.Obtain final products (anode composite material).The present embodiment is made
Anode composite material granularity be 360nm.
Anode composite material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 5C current density, chemical property is tested.Under 5C current density, specific capacity is 25mAh/g, after the circle of circulation 50, only
16mAh/g specific capacity can be kept.Almost without capacity after the circle of circulation 100.The material that this is prepared is due to the ascorbic acid of addition
Excessively, cause pH value of solution relatively low, material carbon content is too high, cause that the amount of active material is less, specific capacity is relatively low.
Comparative example 5
Weigh respectively 0.01mol cobalt chlorides, 0.005mol sodium oxalates and 0.02mol ammonium dihydrogen phosphate be dissolved in 80ml go from
In sub- water, 0.02mol citric acids are added afterwards in above-mentioned solution, regulation pH=4 stirs to form homogeneous solution, afterwards will
0.15g graphene dispersions are in above-mentioned solution.By the aqueous solution as gel is thermally formed in 80 ° of water-baths, it is transferred to afterwards
Presoma is dried to obtain into vacuum drying oven.Finally above-mentioned presoma is ground, under an argon atmosphere, 700 DEG C of sintering 7h, heating
15 DEG C/min of speed.Finally product is cleaned, dried.Obtain final products (anode composite material).The present embodiment is made
Anode composite material granularity be 270nm.
Anode composite material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 5C current density, chemical property is tested.Under 5C current density, specific capacity is reached after 23mAh/g, the circle of circulation 50,
Only keep 13mAh/g specific capacity.Zero is almost decayed to after the circle of circulation 100.The material that this is prepared is due to sodium source in raw material
Ratio not enough, causes that the impurity of material is excessive, and the increase of inert matter causes material specific capacity poor.
Comparative example 6
Weigh respectively 0.01mol cobalt carbonates, 0.005mol sodium oxalates and 0.02mol ammonium dihydrogen phosphate be dissolved in 80ml go from
In sub- water, 0.01mol citric acids are added afterwards in above-mentioned solution, regulation pH=4.5 stirs to form homogeneous solution, afterwards will
0.2g graphene dispersions are in above-mentioned solution.By the aqueous solution as gel is thermally formed in 80 ° of water-baths, it is transferred to afterwards
Presoma is dried to obtain in vacuum drying oven.Finally above-mentioned presoma is ground, under an argon atmosphere, 700 DEG C of sintering 7h, heating speed
Spend 15 DEG C/min.Finally product is cleaned, dried.Obtain final products (anode composite material).Made from the present embodiment
Anode composite material granularity is 270nm.
Anode composite material manufactured in the present embodiment is used for working electrode, sodium is, to electrode, to be assembled into button cell,
Under 5C current density, chemical property is tested.Under 5C current density, specific capacity is reached after 23mAh/g, the circle of circulation 50,
Only keep 13mAh/g specific capacity.Zero is almost decayed to after the circle of circulation 100.This prepare material due to oxide spinel cobalt not
Can substantially uniformity dissolving in aqueous, cause that the impurity of material is excessive, material specific capacity is poor.
Claims (10)
1. a kind of pyrophosphoric acid cobalt sodium/carbon graphite alkene anode composite material, it is characterised in that：Using graphene as substrate, in graphene
Three-dimensional network in be compounded with the composite of pyrophosphoric acid cobalt sodium@carbon.
2. pyrophosphoric acid cobalt sodium as claimed in claim 1/carbon graphite alkene anode composite material, it is characterised in that：Described positive pole
Composite particle diameter is 100-900nm, and graphene accounts for anode composite material mass percent for 5-20%.
3. a kind of preparation method of pyrophosphoric acid cobalt sodium/carbon graphite alkene anode composite material described in claim 1 or 2, its feature
It is：Cobalt source, sodium source, phosphorus source are dissolved in deionized water by the ratio for being 1: 2: 2 in Co, Na, P mol ratio obtains mixed liquor；
Acidic metal complexing reagent is added into mixed liquor, graphene is then added, is heated to forming gel；Gel drying is obtained into forerunner
Body；Presoma is sintered and obtains described anode composite material.
4. the preparation method of pyrophosphoric acid cobalt sodium as claimed in claim 3/carbon graphite alkene anode composite material, it is characterised in that：
It is 2~6 to add acidic metal complexing reagent regulation pH.
5. the preparation method of pyrophosphoric acid cobalt sodium as claimed in claim 3/carbon graphite alkene anode composite material, it is characterised in that：
The cobalt source is at least one of cobalt chloride, cobaltous sulfate, cobalt nitrate, cobalt oxalate, cobalt acetate；
Described sodium source be sodium carbonate, sodium acid carbonate, sodium acetate, sodium oxalate, sodium nitrate, sodium sulphate, niter cake at least
It is a kind of；
Phosphorus source is at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid or pyrophosphoric acid；
In mixed liquor, Co2+Concentration is 0.1-30mol/L, the Na of the solution+Concentration is 0.2-60mol/L, the solution
PO4 3-Concentration is 0.2-60mol/L.
6. the preparation method of the composite positive pole of pyrophosphoric acid cobalt sodium/carbon graphite alkene as claimed in claim 3, its feature exists
In：The acidic metal complexing reagent is at least one in citric acid, ascorbic acid, tartaric acid, ethylenediamine tetra-acetic acid, polyacrylic acid
Kind.
7. the preparation method of pyrophosphoric acid cobalt sodium as claimed in claim 3/carbon graphite alkene anode composite material, it is characterised in that：
The acidic metal complexing reagent and Co of addition2+Mol ratio is 0.5: 1-3: 1.
8. the preparation method of sodium-ion battery anode composite material as claimed in claim 3, it is characterised in that：The graphite of addition
Alkene and the Na of synthesis2CoP2O7Mass ratio be 0.05-0.2: 1.
9. the preparation method of pyrophosphoric acid cobalt sodium as claimed in claim 3/carbon graphite alkene anode composite material, it is characterised in that：
Sintering process is carried out under protective atmosphere, and the temperature of sintering process is 600-800 DEG C.
10. a kind of application of pyrophosphoric acid cobalt sodium/carbon graphite alkene anode composite material described in claim 1 or 2, its feature exists
In the positive pole by described anode composite material for preparing sodium-ion battery.
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