CN108123129A - A kind of carbon coating ferric sodium pyrophosphate material and preparation method thereof and the application as sodium-ion battery positive material - Google Patents
A kind of carbon coating ferric sodium pyrophosphate material and preparation method thereof and the application as sodium-ion battery positive material Download PDFInfo
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Abstract
Application the invention discloses a kind of carbon coating ferric sodium pyrophosphate material and preparation method thereof and as sodium-ion battery positive material, carbon coating ferric sodium pyrophosphate material is in ordered nano-structure, and coated with uniform carbon-coating, its preparation method is by organic polymer surfactant and phosphorus source and hydrocarbon mixture, source of iron and sodium source successively ball milling mixing, obtains presoma；The presoma be placed in protective atmosphere calcine to get.Carbon coating ferric sodium pyrophosphate material is in ordered nano-structure; it is big with electrolyte contacts area; ion diffusion path is short, effectively improves the ion diffusion rates in battery system, and conductive carbon layer effectively promotes the electron transfer rate and stability of electrode material; it is used as sodium-ion battery positive material shows excellent chemical property; it is preferable sodium-ion battery positive material, and its preparation process is simple for process, low cost; the production of scale metaplasia is easily enlarged, there is very big application prospect.
Description
Technical field
The present invention relates to a kind of sodium-ion battery positive materials, and in particular to a kind of carbon coating ferric sodium pyrophosphate material and its
Preparation method and the application as sodium-ion battery positive material；Belong to sodium-ion battery preparing technical field.
Background technology
The world today, the environmental pollution and global warming issue come with the combustion zone of fossil fuel are on the rise, respectively
State is all changed by the economic model based on fossil fuel to based on the economic model based on new energy, Renewable Energy Development
It is a great strategic task of China's economy and social development with clean energy resource.The high speed development of society is to high security, low
The demand of cost energy storage technology is extremely urgent.Lithium ion battery is considered as the most promising energy stores for meeting these demands
One of technology, and successfully apply in portable electric appts, plug-in hybrid-power automobile and pure electric automobile,
It is effectively reduced the CO2 emissions generated during municipal transport.The research of lithium ion battery is mainly collected at present
In develop new high-energy density electrode material, to having, electrode material carries out performance optimization, exploitation high safety performance is consolidated
State electrolyte, negative metal lithium protection technique and battery management system etc..
The Regional Distribution of metal lithium resource is seriously uneven, and metallic sodium is a kind of element that reserves are very abundant on the earth,
And the chemical property similar with lithium metal is shown, show that sodium element can also be applied to similar electrochemical energy storage system.
Twentieth century the seventies and eighties, sodium ion and lithium ion battery are all once by Primary Study.But since the energy of lithium ion battery is close
Higher is spent, is more suitable for small-sized, portable electric appts rechargeable batteries, afterwards a very long time scientific research circle and industry
Sight is all concentrated on lithium ion battery association area by boundary.In recent years, since the reserves of lithium metal are limited and price rising all the way,
And the demand of extensive electrochemistry power grid energy storage technology, the research boom on room temperature sodium-ion battery are rising.Due to
The radius ratio lithium ion of sodium ion is big, and current research key is to find the electrode material that can stablize deintercalation sodium ion.Sodium from
In terms of sub- cell positive material, be concentrated mainly on stratiform transition metal oxide, polyanionic compound, it is Prussian blue and its
The systems such as derivative and organic compound.
In numerous sodium-ion battery positive materials, polyanionic compound is with its excellent structural stability, peace
Full property and suitable voltage platform are considered as a kind of electrode material for most having application prospect.By taking phosphate as an example, it contains spy
The different tetrahedron PO with strong covalent bond4The relative separation of unit, valence electron and polyanion.This special three-dimensional framework
Structure, with polyelectron mechanism, the energy jump between highest occupied molecular orbital and minimum occupied molecular orbital is smaller, very
Be conducive to the quick abjection and insertion of sodium ion.In recent years, it was recently reported that a variety of polyanionic electrode materials, including Na3V2
(PO4)3, NaFePO4, Na2FeP2O7, Na2MnP2O7, Na3M2(PO4)2F3(M=Ti, Fe, V), Na7V4(P2O7)4(PO4),
Na2Fe3-xMnx(PO4)3, Na4Fe3(PO4)2(P2O7) and Na4-aM2+a/2(P2O7)2(2/3≤a≤7/8, M=Fe, Fe0.5Mn0.5,
Mn) etc..
Due to abundant cheap iron resource, three-dimensional ion diffusion admittance, good security performance, ferric sodium pyrophosphate material
More and more favored.Nevertheless, electron conduction is poor, ion diffusion rates are slow, high temperature sintering structure is difficult to control
Remain Na2FeP2O7、Na7Fe4.5(P2O7)4、Na3.12Fe2.44(P2O7)2And Na3.32Fe2.34(P2O7)2Wait ferric sodium pyrophosphates material
Common difficulty.In order to solve problem above, the present invention provides a kind of method for preparing carbon coating ferric sodium pyrophosphate material, mistakes
Journey is simple for process, and product is stablized, and is easily enlarged the production of scale metaplasia, the ferric sodium pyrophosphate well-crystallized of preparation, size uniformity, electricity
Chemical property is excellent, there is very big application prospect.
The content of the invention
For existing ferric sodium pyrophosphate material, there are electron conduction is poor, ion diffusion rates are slow, high temperature sintering structure
The technological deficiencies such as uncontrollable, the purpose of the invention is to provide one kind to have in ordered nano-structure, and surface is uniformly wrapped
Cover conductive carbon layer, the carbon coating ferric sodium pyrophosphate material of electrochemical performance.
Second object of the present invention be to provide it is a kind of it is simple for process, reproducible, inexpensive, be easily enlarged scale
Change the preparation carbon coating ferric sodium pyrophosphate material of metaplasia production.
Third object of the present invention is to be to provide a kind of carbon coating ferric sodium pyrophosphate material as sodium-ion battery just
Pole material application has high specific discharge capacity with the sodium-ion battery of carbon coating ferric sodium pyrophosphate material preparation, and the specific volume that discharges
Measure the advantages that conservation rate is high.
In order to realize above-mentioned technical purpose, the present invention provides a kind of preparation method of carbon coating ferric sodium pyrophosphate material,
This method is by organic polymer surfactant and phosphorus source and hydrocarbon mixture, source of iron and sodium source successively ball milling mixing, is obtained
Presoma；The presoma be placed in protective atmosphere calcine to get.
Preferred scheme, the organic polymer surfactant include hydroxyl, carboxylic acid group, sulfonic group, sulfate, phosphoric acid
At least one of base, amino, amido, ammonium, amide groups, ehter bond hydrophilic radical and C8More than hydrocarbon chain.
Preferred scheme, the high molecular surfactant include oleic acid, enuatrol, stearic acid, odium stearate, citric acid
Sodium, sodium alginate, neopelex, lauryl sodium sulfate, ammonium lauryl sulfate, 1-isobutyl-3,5-dimethylhexylphosphoric acid, ten
Dialkyl dimethyl amine oxide, Span 20, Span 40, Span 60, Span 80, kayexalate, polystyrene maleic acid
Anhydride copolymer, amino acid pattern glyceride, fatty alcohol, fatty alcohol sodium isethionate, aliphatic acid sulfoalkyl ester and aliphatic acid sulphur alkane
At least one of base amide.
Preferred scheme, hydrocarbon mixture include at least one of solid paraffin, vaseline, atoleine.Atoleine
Such as paraffin oil, white oil, dormant oil, vaseline such as mineral fat, soft paraffin etc., solid paraffin such as mineral tallow etc..
Preferred scheme, phosphorus source include ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, phosphoric acid, biphosphate
At least one of sodium, disodium hydrogen phosphate, phosphorus pentoxide, microcosmic salt, pyrophosphoric acid, sodium pyrophosphate, ortho phosphorous acid.
Preferred scheme, the source of iron include ferrous sulfate, ammonium ferric sulfate, iron ammonium sulfate, ferrous oxalate, oxalic acid high ferro
In ammonium, iron oxide, ferroso-ferric oxide, frerrous chloride, iron hydroxide, ironic citrate, ferric citrate, ferric phosphate, ferric nitrate extremely
Few one kind.
Preferred scheme, the sodium source include anhydrous sodium acetate, sodium hydroxide, sodium carbonate, sodium oxalate, sodium nitrite, phosphorus
Sour disodium hydrogen, sodium acid carbonate, sodium citrate, anhydrous sodium sulfate, odium stearate, enuatrol, sodium tartrate, sodium alginate, carboxylic first
At least one of base sodium cellulosate, sodium lactate, sodium humate.
The molar ratio of preferred scheme, the organic polymer surfactant and phosphorus source is 0.2~3:1.
The mass ratio of preferred scheme, the hydrocarbon mixture and organic polymer surfactant is 0.5~3:1.
Preferred scheme, the molar ratio of phosphorus source, source of iron and sodium source is according to the molecular formula of the ferric sodium pyrophosphate of generation come really
It is fixed；The molecular formula of the ferric sodium pyrophosphate is NaFeP2O7、Na2FeP2O7、Na7Fe3(P2O7)4Or NaαFeβP2O7, wherein 1 ＜ α/βs
＜ 2.For example, for NaFeP2O7, the molar ratio of sodium source, source of iron and phosphorus source is with the molar ratio of sodium ion, iron ion and pyrophosphate
For 1~1.1:1:1 metering；For Na2FeP2O7, the molar ratio of sodium source, source of iron and phosphorus source is with sodium ion, iron ion and pyrophosphoric acid
The molar ratio of root is 2~2.2:1:1 metering；For Na7Fe3(P2O7)4, the molar ratio of sodium source, source of iron and phosphorus source is with sodium ion, iron
The molar ratio of ion and pyrophosphate is 7~7.7:3:4 meterings.
Preferred scheme, the presoma are placed under protective atmosphere, are risen to the heating rate of 1 DEG C/1in~10 DEG C/1in
500 DEG C~900 DEG C, heat preservation 2 it is small when~18 it is small when.
Preferred scheme, the protective atmosphere include nitrogen and/or inert gas or nitrogen and/or inert gas with
Reducibility gas mixes.Further preferred scheme, protective atmosphere mix for nitrogen and/or inert gas with reducibility gas
When, reducibility gas is hydrogen, carbon monoxide or hydrogen and carbon mono oxide mixture, and wherein reducibility gas is in gaseous mixture
Volume percent content is 3~15%.
The present invention also provides a kind of carbon coating ferric sodium pyrophosphate materials, are obtained by the preparation method.
It, should as sodium ion positive electrode the present invention also provides a kind of application of carbon coating ferric sodium pyrophosphate material
With.
Carbon coating ferric sodium pyrophosphate material prepared by technical scheme has the knot in ordered nano laminated structure
The ferric pyrophosphate sodium crystal and electrolyte contacts area of structure are big, and ion diffusion path is short, effectively improve in battery system from
Sub- diffusion rate；Ferric sodium pyrophosphate plane of crystal is uniformly coated with conductive carbon layer, effectively promotes the electron-transport speed of electrode material
Rate, while improve the stability of material.Carbon coating ferric sodium pyrophosphate material has excellent chemical property, is sodium ion electricity
The preferable electrode material in pond.
Technical scheme key in carbon coating ferric sodium pyrophosphate materials process is synthesized is to mix using hydro carbons
The crystal morphology for being capable of Effective Regulation ferric sodium pyrophosphate is applied in combination in object and organic polymer surfactant, the two.Hydro carbons mixes
Close benign organic solvent of the object as organic polymer surfactant, in hydrocarbon mixture melting media, organic polymer
Surfactant has chelation to metal ion, and passes through crystal self assembly, obtains ordered nano-structure ferric sodium pyrophosphate
Crystal (as shown in figures 5-8), this ordered nano-structure material and electrolyte contacts area are big, and ion diffusion path is short, effectively
Improve the ion diffusion rates in battery system.Hydrocarbon mixture and organic polymer surfactant are used as carbon simultaneously
Source to the ferric pyrophosphate sodium crystal in-stiu coating carbon of generation, greatly improves the electric conductivity and stability of ferric sodium pyrophosphate material.
Technical scheme is uniform by phosphorus source, source of iron, sodium source and surfactant using high-energy ball milling method first
It is blended in hydrocarbon mixture (such as mineral oil, vaseline or Wax dielectric), uniformly mixes presoma directly in protective atmosphere
Target product is obtained after calcining --- carbon coating ferric sodium pyrophosphate material；The preparation side of specific carbon coating ferric sodium pyrophosphate material
Method comprises the following steps：
(1) organic polymer surfactant and phosphorus source are added in ball grinder by a certain percentage, adds in ball-milling medium, ball
Certain time is ground, obtains opalescent mixture；
(2) a certain proportion of organic solvent mineral oil or wax are added in the ball grinder into step (1), continues ball milling one
It fixes time；
(3) source of iron is added in the ball grinder into step (2), continues ball milling certain time, obtains mixture of viscous form；
(4) sodium source is added in the ball grinder into step (3), continues ball milling certain time, obtains thick uniform mixing
Presoma；
(5) obtained uniform mixing presoma in step (4) is calcined in protective atmosphere, furnace cooling, gained production
Object is carbon ferric sodium pyrophosphate material；
Ball grinder in step (1) is stainless steel jar mill, PA6 nylon ball grinders, corundum ceramic ball grinder, polyurethane ball
Any one of grinding jar, polytetrafluoroethylene (PTFE) ball grinder, zirconia ball grinding jar, hard alloy ball grinder, the volume of ball grinder is 30
Milliliter~2.5 liters；The ball-milling medium for 304 stainless steel balls, agate ball, corundum ball, polyurethane ball, polytetrafluoroethylene (PTFE) ball,
Any one in zirconia ball, sintered carbide ball, a diameter of 1 millimeter~12 millimeters；
In step (1), step (2), step (3) and step (4) Ball-milling Time for 0.5 it is small when~24 it is small when, the speed of ball milling
It spends for 600 revs/min~1500 revs/min.
Compared with the prior art, technical scheme has the following advantages that：
1. the carbon coating ferric sodium pyrophosphate material of the present invention has ordered nano-structure；This nano structural material and electrolysis
Liquid contact area is big, and ion diffusion path is short, effectively improves the ion diffusion rates in battery system.
2. the carbon coating ferric sodium pyrophosphate material of the present invention is coated with uniform conductive carbon layer on nanocrystal surface, effectively
It improves the electronics conduction efficiency of electrode material and improves the stability of ferric sodium pyrophosphate material.
3. the present invention synthesizes carbon coating ferric pyrophosphate using hydrocarbon mixture and organic polymer surfactant system
Sodium material, in hydrocarbon mixture melting media, by the chelation of organic polymer surfactant, by crystal from group
Dress, to obtain the ferric pyrophosphate sodium crystal of ordered nano-structure, while hydrocarbon mixture and organic polymer surfactant are made
Uniform clad is obtained in ferric sodium pyrophosphate plane of crystal for carbon source, greatly improves the chemical property of composite material.
4. the present invention prepares hydrocarbon mixture and the organic polymer surface-active that carbon coating ferric sodium pyrophosphate material uses
Agent is cheap, and preparation process is simple for process, and safety and environmental protection is of low cost.
5. carbon coating ferric sodium pyrophosphate material prepared by the present invention has excellent chemical property, as sodium-ion battery
Positive electrode can discharge 89.8 1A h g under the current density of 0.2C-1Specific discharge capacity, discharge after charge and discharge 200 times
Specific capacity still can keep 92.3%, be the preferable electrode material of sodium-ion battery.
Description of the drawings
【Fig. 1】The carbon coating Na prepared for embodiment 13.12Fe2.44(P2O7)2The XRD spectrum of dusty material；
【Fig. 2】The carbon coating Na prepared for embodiment 23.12Fe2.44(P2O7)2The XRD spectrum of dusty material；
【Fig. 3】The carbon coating Na prepared for embodiment 33.12Fe2.44(P2O7)2The XRD spectrum of dusty material；
【Fig. 4】The carbon coating Na prepared for embodiment 72FeP2O7The XRD spectrum of dusty material；
【Fig. 5】The carbon coating Na prepared for embodiment 23.12Fe2.44(P2O7)2The SEM spectrum of dusty material；
【Fig. 6】The carbon coating Na prepared for embodiment 43.12Fe2.44(P2O7)2The SEM spectrum of dusty material；
【Fig. 7】The carbon coating Na prepared for embodiment 93.12Fe2.44(P2O7)2The SEM spectrum of dusty material；
【Fig. 8】The carbon coating Na prepared for embodiment 82FeP2O7The SEM spectrum of dusty material；
【Fig. 9】The carbon coating Na prepared for embodiment 23.12Fe2.44(P2O7)2The sodium ion half-cell that dusty material is assembled into
Under the current density of 0.2C, the cycle performance figure in the voltage window of 1.5V~4V, wherein 1C=1201A g-1；
【Figure 10】The carbon coating Na prepared for embodiment 43.12Fe2.44(P2O7)2Half electricity of the sodium ion that dusty material is assembled into
Pond is under the current density of 0.2C, the cycle performance figure in the voltage window of 1.5V~4V, wherein 1C=1201A g-1。
Specific embodiment
Present invention is intended to further illustrate with reference to embodiments, the claim that is not intended to limit the present invention protection model
It encloses.
Embodiment 1
2.3236g ammonium dihydrogen phosphates and 8.6467g oleic acid are added in the stainless steel jar mill of 501l, add in a diameter of 2
Millimeter and 4 millimeters of each 20 of 304 stainless steel balls as ball-milling medium, with high-energy mechanical ball milling machine ball milling mixing 2 it is small when, obtain
Opalescent mixture.11.529g paraffin waxs are added in, when then ball milling mixing 1 is small.Then it is sub- that bis- oxalic acid hydrates of 2.216g are added in
Iron when continuation ball milling mixing 1 is small, obtains clear yellow viscous mixture.1.2926g anhydrous sodium acetates are eventually adding, ball milling mixing 2 is small
When, obtain thick uniform mixing presoma.The thick presoma of ferric sodium pyrophosphate is gone to and is connected with H2/ Ar (Ar and H2Volume ratio
For 95:5) in the quartz tube furnace of mixed gas, 600 DEG C of calcining at constant temperature 12h, furnace cooling are risen to 2 DEG C/1in heating rates
Obtain carbon coating Na3.12Fe2.44(P2O7)2Dusty material.It is analyzed using Rigaku D/1ax-2500 type X-ray diffraction analysis instrument
The crystal structure of gained sample, acquired results are as shown in Figure 1.
Embodiment 2
2.3236g ammonium dihydrogen phosphates and 8.6467g oleic acid are added in the stainless steel jar mill of 501l, add in a diameter of 2
Millimeter and 4 millimeters of each 20 of 304 stainless steel balls as ball-milling medium, with high-energy mechanical ball milling machine ball milling mixing 2 it is small when, obtain
Opalescent mixture.11.529g paraffin waxs are added in, when then ball milling mixing 1 is small.Then it is sub- that bis- oxalic acid hydrates of 2.216g are added in
Iron when continuation ball milling mixing 1 is small, obtains clear yellow viscous mixture.1.2926g anhydrous sodium acetates are eventually adding, ball milling mixing 2 is small
When, obtain thick uniform mixing presoma.The thick presoma of ferric sodium pyrophosphate is gone to and is connected with H2/ Ar (Ar and H2Volume ratio
For 95:5) in the quartz tube furnace of mixed gas, 650 DEG C of calcining at constant temperature 12h, furnace cooling are risen to 2 DEG C/1in heating rates
Obtain carbon coating Na3.12Fe2.44(P2O7)2Dusty material.It is analyzed using Rigaku D/1ax-2500 type X-ray diffraction analysis instrument
The crystal structure of gained sample, acquired results are as shown in Figure 2.Use 230 scanning electron microscope of FEI Co. of U.S. Nova NanoSEM
The pattern of sample is observed, it is found that sample is assembled by nanometer sheet, as shown in Figure 5.Cycle performance test voltage scope is
1.5V~4V, current density 0.2C, its specific capacity is still up to 78.9 1A h g after cycling 200 times-1.Its cycle performance result
As shown in Figure 9
Embodiment 3
2.3236g ammonium dihydrogen phosphates and 8.6467g oleic acid are added in the stainless steel jar mill of 501l, add in a diameter of 2
Millimeter and 4 millimeters of each 20 of 304 stainless steel balls as ball-milling medium, with high-energy mechanical ball milling machine ball milling mixing 2 it is small when, obtain
Opalescent mixture.11.529g paraffin waxs are added in, when then ball milling mixing 1 is small.Then it is sub- that bis- oxalic acid hydrates of 2.216g are added in
Iron when continuation ball milling mixing 1 is small, obtains clear yellow viscous mixture.1.2926g anhydrous sodium acetates are eventually adding, ball milling mixing 2 is small
When, obtain thick uniform mixing presoma.The thick presoma of ferric sodium pyrophosphate is gone to and is connected with H2/ Ar (Ar and H2Volume ratio
For 95:5) in the quartz tube furnace of mixed gas, 700 DEG C of calcining at constant temperature 12h, furnace cooling are risen to 2 DEG C/1in heating rates
Obtain carbon coating Na3.12Fe2.44(P2O7)2Dusty material.It is analyzed using Rigaku D/1ax-2500 type X-ray diffraction analysis instrument
The crystal structure of gained sample, acquired results are as shown in Figure 3.
Embodiment 4
2.3236g ammonium dihydrogen phosphates and 11.529g oleic acid are added in the stainless steel jar mill of 501l, add in a diameter of 2
Millimeter and 4 millimeters of each 20 of 304 stainless steel balls as ball-milling medium, with high-energy mechanical ball milling machine ball milling mixing 2 it is small when, obtain
Opalescent mixture.11.529g paraffin waxs are added in, when then ball milling mixing 1 is small.Then it is sub- that bis- oxalic acid hydrates of 2.216g are added in
Iron when continuation ball milling mixing 1 is small, obtains clear yellow viscous mixture.1.2926g anhydrous sodium acetates are eventually adding, ball milling mixing 2 is small
When, obtain thick uniform mixing presoma.The thick presoma of ferric sodium pyrophosphate is gone to and is connected with H2/ Ar (Ar and H2Volume ratio
For 95:5) in the quartz tube furnace of mixed gas, 650 DEG C of calcining at constant temperature 12h, furnace cooling are risen to 2 DEG C/1in heating rates
Obtain carbon coating Na3.12Fe2.44(P2O7)2Dusty material.Use 230 scanning electron microscopic observations of FEI Co. of U.S. Nova NanoSEM
The pattern of sample finds that sample is assembled by nanometer sheet, as shown in Figure 6.Cycle performance test voltage scope for 1.5V~
4V, current density 0.2C, its specific capacity is still up to 82.9 1A h g after cycling 200 times-1.Its cycle performance result such as Figure 10
It is shown
Embodiment 5
2.3236g ammonium dihydrogen phosphates and 11.529g oleic acid are added in the stainless steel jar mill of 501l, add in a diameter of 2
Millimeter and 4 millimeters of each 20 of 304 stainless steel balls as ball-milling medium, with high-energy mechanical ball milling machine ball milling mixing 2 it is small when, obtain
Opalescent mixture.11.529g paraffin waxs are added in, when then ball milling mixing 1 is small.Then bis- oxalic acid hydrates of 1.8171g are added in
Ferrous iron when continuation ball milling mixing 1 is small, obtains clear yellow viscous mixture.It is eventually adding 1.7069g anhydrous sodium acetates, ball milling mixing 2
Hour, obtain thick uniform mixing presoma.The thick presoma of ferric sodium pyrophosphate is gone to and is connected with H2/ Ar (Ar and H2Volume
Than for 95:5) in the quartz tube furnace of mixed gas, 600 DEG C of calcining at constant temperature 12h are risen to 2 DEG C/1in heating rates, with furnace cooling
But carbon coating Na is obtained2FeP2O7Dusty material.
Embodiment 6
2.3236g ammonium dihydrogen phosphates and 11.529g oleic acid are added in the stainless steel jar mill of 501l, add in a diameter of 2
Millimeter and 4 millimeters of each 20 of 304 stainless steel balls as ball-milling medium, with high-energy mechanical ball milling machine ball milling mixing 2 it is small when, obtain
Opalescent mixture.11.529g paraffin waxs are added in, when then ball milling mixing 1 is small.Then bis- oxalic acid hydrates of 1.8171g are added in
Ferrous iron when continuation ball milling mixing 1 is small, obtains clear yellow viscous mixture.It is eventually adding 1.7069g anhydrous sodium acetates, ball milling mixing 2
Hour, obtain thick uniform mixing presoma.The thick presoma of ferric sodium pyrophosphate is gone to and is connected with H2/ Ar (Ar and H2Volume
Than for 95:5) in the quartz tube furnace of mixed gas, 650 DEG C of calcining at constant temperature 12h are risen to 2 DEG C/1in heating rates, with furnace cooling
But carbon coating Na is obtained2FeP2O7Dusty material.
Embodiment 7
2.3236g ammonium dihydrogen phosphates and 11.529g oleic acid are added in the stainless steel jar mill of 501l, add in a diameter of 2
Millimeter and 4 millimeters of each 20 of 304 stainless steel balls as ball-milling medium, with high-energy mechanical ball milling machine ball milling mixing 2 it is small when, obtain
Opalescent mixture.11.529g paraffin waxs are added in, when then ball milling mixing 1 is small.Then bis- oxalic acid hydrates of 1.8171g are added in
Ferrous iron when continuation ball milling mixing 1 is small, obtains clear yellow viscous mixture.It is eventually adding 1.7069g anhydrous sodium acetates, ball milling mixing 2
Hour, obtain thick uniform mixing presoma.The thick presoma of ferric sodium pyrophosphate is gone to and is connected with H2/ Ar (Ar and H2Volume
Than for 95:5) in the quartz tube furnace of mixed gas, 300 DEG C of calcining at constant temperature 6h is risen to 2 DEG C/1in heating rates and are warming up to again
600 DEG C of calcining at constant temperature 12h, furnace cooling obtain carbon coating Na2FeP2O7Dusty material.Using Rigaku D/1ax-2500 types X
The crystal structure of x ray diffraction analysis x instrument analysis gained sample, acquired results are as shown in Figure 4.
Embodiment 8
2.3236g ammonium dihydrogen phosphates and 17.2935g oleic acid are added in the stainless steel jar mill of 501l, add in a diameter of 2
Millimeter and 4 millimeters of each 20 of 304 stainless steel balls as ball-milling medium, with high-energy mechanical ball milling machine ball milling mixing 2 it is small when, obtain
Opalescent mixture.11.529g paraffin waxs are added in, when then ball milling mixing 1 is small.Then bis- oxalic acid hydrates of 1.8171g are added in
Ferrous iron when continuation ball milling mixing 1 is small, obtains clear yellow viscous mixture.It is eventually adding 1.7069g anhydrous sodium acetates, ball milling mixing 2
Hour, obtain thick uniform mixing presoma.The thick presoma of ferric sodium pyrophosphate is gone to and is connected with H2/ Ar (Ar and H2Volume
Than for 95:5) in the quartz tube furnace of mixed gas, 300 DEG C of calcining at constant temperature 6h is risen to 2 DEG C/1in heating rates and are warming up to again
600 DEG C of calcining at constant temperature 12h, furnace cooling obtain carbon coating Na2FeP2O7Dusty material.Use FEI Co. of U.S. Nova
The pattern of 230 scanning electron microscopic observation samples of NanoSEM finds that sample is assembled by nanometer sheet, as shown in Figure 8.
Embodiment 9
2.3236g ammonium dihydrogen phosphates and 12.858g Spans 80 are added in the stainless steel jar mill of 501l, added in a diameter of
2 millimeters and 4 millimeters of each 20 of 304 stainless steel balls as ball-milling medium, with high-energy mechanical ball milling machine ball milling mixing 2 it is small when, obtain
To opalescent mixture.12.858g paraffin waxs are added in, when then ball milling mixing 1 is small.Then add in 2.2169g bis- and be hydrated grass
It is sour ferrous, when continuation ball milling mixing 1 is small, obtain clear yellow viscous mixture.1.3314g anhydrous sodium acetates are eventually adding, ball milling mixes
Close 2 it is small when, obtain thick uniform mixing presoma.The thick presoma of ferric sodium pyrophosphate is gone to and is connected with H2/ Ar (Ar and H2
Volume ratio is 95:5) in the quartz tube furnace of mixed gas, 650 DEG C of calcining at constant temperature 12h are risen to 2 DEG C/1in heating rates, with
Furnace cooling but obtains carbon coating Na3.12Fe2.44(P2O7)2Dusty material.Electricity is scanned using FEI Co. of U.S. Nova NanoSEM 230
The pattern of sem observation sample finds that sample is assembled by nanometer sheet, as shown in Figure 7.
Embodiment 10
2.3236g ammonium dihydrogen phosphates and 12.858g Spans 80 are added in the stainless steel jar mill of 501l, added in a diameter of
2 millimeters and 4 millimeters of each 20 of 304 stainless steel balls as ball-milling medium, with high-energy mechanical ball milling machine ball milling mixing 2 it is small when, obtain
To opalescent mixture.12.858g paraffin waxs are added in, when then ball milling mixing 1 is small.Then add in 1.8171g bis- and be hydrated grass
It is sour ferrous, when continuation ball milling mixing 1 is small, obtain clear yellow viscous mixture.1.7069g anhydrous sodium acetates are eventually adding, ball milling mixes
Close 2 it is small when, obtain thick uniform mixing presoma.The thick presoma of ferric sodium pyrophosphate is gone to and is connected with H2/ Ar (Ar and H2
Volume ratio is 95:5) in the quartz tube furnace of mixed gas, 300 DEG C of calcining at constant temperature 6h is risen to 2 DEG C/1in heating rates and are risen again
Temperature to 600 DEG C of calcining at constant temperature 12h, furnace cooling obtains carbon coating Na2FeP2O7Dusty material.
Embodiment 11
Carbon coating ferric sodium pyrophosphate material prepared by embodiment 2 and embodiment 4, conductive carbon Super P and poly- inclined difluoro second
Alkene (PVDF) binding agent is according to 8:1:1 mass ratio after mixing, be dispersed in N- methyl pyrroles obtain in alkanone (NMP) solution
Starchy mixture.The paste mixture of acquisition is uniformly coated on aluminium foil, and when 100 DEG C of vacuum drying 12 are small.
The assembling of ferric sodium pyrophosphate sodium button cell (2016 model) be in the glove box (German Braun) full of high-purity argon gas into
Row.Using metallic sodium piece as cathode, using glass fibre as membrane, 1M NaClO4It is dissolved in propene carbonate/fluoro ethylene carbonate
Ester (PC/FEC) (1:1, volume ratio) as electrolyte, the anode material of the carbon coating ferric sodium pyrophosphate material of synthesis as battery
Material.The charging and discharging test of sodium-ion battery carries out on blue electric battery test system at room temperature, the voltage range of test
It is 1.5V~4V references in Na/Na+。
Claims (10)
1. a kind of preparation method of carbon coating ferric sodium pyrophosphate material, it is characterised in that：By organic polymer surfactant and
Phosphorus source and hydrocarbon mixture, source of iron and sodium source successively ball milling mixing, obtain presoma；The presoma, which is placed in protective atmosphere, to be forged
Burn to get.
2. a kind of preparation method of carbon coating ferric sodium pyrophosphate material according to claim 1, it is characterised in that：It is described to have
Machine high molecular surfactant include hydroxyl, carboxylic acid group, sulfonic group, sulfate, phosphate, amino, amido, ammonium, amide groups,
At least one of ehter bond hydrophilic radical and C8More than hydrocarbon chain.
3. a kind of preparation method of carbon coating ferric sodium pyrophosphate material according to claim 2, it is characterised in that：The height
Molecular surface active agent includes oleic acid, enuatrol, stearic acid, odium stearate, sodium citrate, sodium alginate, detergent alkylate sulphur
Sour sodium, lauryl sodium sulfate, ammonium lauryl sulfate, 1-isobutyl-3,5-dimethylhexylphosphoric acid, dodecyldimethylamine oxide, Span
20th, Span 40, Span 60, Span 80, kayexalate, polystyrene maleic anhydride copolymer, amino acid pattern glyceride,
At least one of fatty alcohol, fatty alcohol sodium isethionate, aliphatic acid sulfoalkyl ester and aliphatic acid sulfoalkyl amide.
4. a kind of preparation method of carbon coating ferric sodium pyrophosphate material according to claim 1, it is characterised in that：Hydro carbons mixes
Closing object includes at least one of solid paraffin, vaseline, atoleine.
5. a kind of preparation method of carbon coating ferric sodium pyrophosphate material according to claim 1, it is characterised in that：The phosphorus
Source includes ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, phosphorus pentoxide, phosphorus
At least one of sour hydrogen sodium ammonium, pyrophosphoric acid, sodium pyrophosphate, ortho phosphorous acid；The source of iron includes ferrous sulfate, ammonium ferric sulfate, sulphur
Sour ferrous ammonium, ferrous oxalate, ammonium ferric oxalate, iron oxide, ferroso-ferric oxide, frerrous chloride, iron hydroxide, ironic citrate, lemon
At least one of lemon acid iron ammonium, ferric phosphate, ferric nitrate；
The sodium source includes anhydrous sodium acetate, sodium hydroxide, sodium carbonate, sodium oxalate, sodium nitrite, disodium hydrogen phosphate, bicarbonate
Sodium, sodium citrate, anhydrous sodium sulfate, odium stearate, enuatrol, sodium tartrate, sodium alginate, sodium carboxymethylcellulose, lactic acid
At least one of sodium, sodium humate.
6. according to a kind of preparation method of carbon coating ferric sodium pyrophosphate material of Claims 1 to 5 any one of them, feature exists
In：The molar ratio of the organic polymer surfactant and phosphorus source is 0.2~3:1；
The mass ratio of the hydrocarbon mixture and organic polymer surfactant is 0.5~3:1；
The molar ratio of phosphorus source, source of iron and sodium source is determined according to the molecular formula of the ferric sodium pyrophosphate of generation；The ferric pyrophosphate
The molecular formula of sodium is NaFeP2O7、Na2FeP2O7、Na7Fe3(P2O7)4Or NaαFeβP2O7, wherein 1 ＜ α/βs ＜ 2.
7. according to a kind of preparation method of carbon coating ferric sodium pyrophosphate material of claims 1 to 3 any one of them, feature exists
In：The presoma is placed under protective atmosphere, is risen to 500 DEG C~900 DEG C with 1 DEG C/111~10 DEG C/111 heating rate, is protected
Temperature 2 it is small when~18 it is small when.
8. a kind of preparation method of carbon coating ferric sodium pyrophosphate material according to claim 7, it is characterised in that：The guarantor
Shield atmosphere includes nitrogen and/or inert gas or nitrogen and/or inert gas is mixed with reducibility gas.
9. a kind of carbon coating ferric sodium pyrophosphate material, it is characterised in that：It is obtained by any one of claim 1~9 preparation method
It arrives.
10. a kind of application of carbon coating ferric sodium pyrophosphate material described in claim 9, it is characterised in that：As sodium ion just
Pole material application.
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