CN108232118A - A kind of preparation method of FeP/ nitrogen, phosphor codoping graphene electrochemistry storage sodium combination electrode - Google Patents
A kind of preparation method of FeP/ nitrogen, phosphor codoping graphene electrochemistry storage sodium combination electrode Download PDFInfo
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses the preparation methods of a kind of FeP/ nitrogen, phosphor codoping graphene electrochemistry storage sodium combination electrode, and the invention belongs to electrochemical fields;Specific steps:S1, graphene oxide are added to the water, and graphene oxide solution is obtained after ultrasound;S2, appropriate source of iron is taken to be added in graphene oxide solution, adds itrogenous organic substance, ultrasound carries out hydro-thermal reaction, cools down, and washs, dry, and FeP/ nitrogen, phosphor codoping graphene is prepared in phosphorating treatment;Combination electrode is made by S3 for the composite nano materials that S2 is obtained.The present invention is using graphene oxide, source of iron and itrogenous organic substance as raw material, by the way that the methods of hydro-thermal and freeze-drying successfully prepares FeP/ nitrogen, phosphor codoping graphene stores up sodium combination electrode, this method is of low cost, and energy consumption is relatively low, nano particle is evenly distributed, and has excellent sodium ion performance.
Description
Technical field
The invention belongs to electrochemical fields, and in particular to a kind of FeP/ nitrogen, phosphor codoping graphene electrochemistry storage sodium are compound
The preparation method of electrode.
Background technology
With the development of accumulation power supply and electric vehicle power sources, sodium-ion battery is cheap because its is resourceful, safety
Can be good, the advantages such as stable electrochemical property become the hot spot of Recent study.However the commercialization of anode material of lithium-ion battery
Some problems are faced, since the radius of sodium ion radius ratio lithium ion is big by 42%, the lithium ion battery negative material of traditional commodities
The insertion and abjection of sodium ion are not appropriate for, exploitation high power capacity, high circulation stability, the negative material with superperformance become
It is particularly significant.
Transition metal phosphide shows huge prospect in sodium-ion battery, because in their abundant natural contents and
High theoretical sodium is from storage volume.These advantages meet well next-generation sodium ion negative material high-energy density and into
This cheap needs.However, since sodium ion and metal phosphide generate huge irreversible volume change during sodium
(More than 300%), so as to cause the crushing and reunion of active material on electrode, eventually lead in the inactivation and battery of active material
The increase of resistance.Forefathers' research shows that, by electrode material assemble formation of nanostructured or it is compound with carbon material be effective
Approach promote their performances in sodium-ion battery.The conducting path that nanostructured can shorten sodium ion alleviates activity
The structure and volume change of material, while the contact area of electrode and electrolyte can also be increased, increase reaction site and reaction is lived
Property.Compound carbon material can come the reunion and crushing of restricted activity substance as buffer layer, while can also provide good conduction
Property.FeP nano-particles are prepared at present and its melamine, soluble carbon source is usually used with the technology of graphene composite material
It is generated under the induction of " two-dimensional nano reactor " formed in situ and restriction effect with soluble metal molysite, but utilizes and contain
Nitrogen organic prepares FeP/ not only as reducing agent but also as bonding agent using technologies such as simple step hydro-thermal and freeze-dryings
The method that nitrogen, phosphor codoping graphene electrochemistry store up sodium combination electrode has not been reported.In addition, in order to improve the electrification of graphene
Performance is learned, by adulterating the hetero atoms such as other heteroatoms such as nitrogen (N), phosphorus (P), boron (B), sulphur (S) in graphene, increases stone
Black alkene interlamellar spacing improves local electronic structure and electronic conductivity to enhance its storage sodium performance.
Invention content
Poor, the volume in battery charging and discharging cyclic process for anode material of lithium-ion battery electric conductivity traditional at present
Expansion cause powder come off its special capacity fade it is too fast the deficiencies of, the present invention proposes FeP/ nitrogen, phosphor codoping graphene electrochemistry
The preparation method of sodium combination electrode is stored up, the structural stability and chemical property of anode material of lithium-ion battery can be improved, is improved
Cycle performance and high rate performance of the material under charge and discharge process, the combination electrode has high electrochemistry storage sodium capacity, excellent
Different cycle performance and the characteristic of enhancing multiplying power, are with a wide range of applications.
The purpose of the present invention is achieved through the following technical solutions:
Present invention firstly provides a kind of FeP/ nitrogen, phosphor codoping graphene electrochemistry storage sodium combination electrode, the compound electric is great
There is the redox graphene black gel of three-dimensional structure, graphene surface In-situ reaction there are FeP particles;The FeP nanometers
Particle uniformity, grain size are 30 ~ 80 nm;Graphene is modified graphene, surface and interlayer doped with nitrogen, phosphorus atoms.
The present invention also provides the preparation method of a kind of FeP/ nitrogen, phosphor codoping graphene electrochemistry storage sodium combination electrode, packets
Include following steps:
S1. graphene oxide is dispersed in water, graphene oxide solution is obtained after ultrasound;
S2. a certain amount of source of iron is added into the graphene oxide solution described in S1, organic compounds containing nitrogen ultrasound is added in and mixes
It is even, hydro-thermal reaction is carried out, freeze-drying process is carried out after natural cooling, obtains nitrogenous graphene hydrogel;Then, phosphatization is added in
Agent is placed in tube furnace, is passed through nitrogen or argon gas is made annealing treatment, obtain composite nano materials;
S3. sodium active material is stored up using the composite nano materials described in S2 as electrochemistry, is mixed with acetylene black, binding agent,
Uniform slurry is tuned into, is applied on the copper foil as collector, dry, rolling obtains FeP/ nitrogen, phosphor codoping graphene electricity
Chemistry storage sodium combination electrode.
Preferably, a concentration of 15 g/ml of the graphene oxide described in S1.
Preferably, the mass ratio of the source of iron described in S2 and graphene is 1:1~4:1, organic compounds containing nitrogen and graphene
Molar ratio is 1:1~2:1.
Preferably, the source of iron described in S2 is frerrous chloride, Iron(III) chloride hexahydrate, six nitric hydrate iron and their knot
It is one or more in brilliant hydrate.
Preferably, the organic compounds containing nitrogen described in S2 be ethylenediamine, melamine, ammonium hydroxide it is therein one or more.
Preferably, the hydrothermal temperature described in S2 is 60 DEG C ~ 90 DEG C, and the time is 10 ~ 20 h;The temperature of the freeze-drying
It is -50 ~ -20 DEG C to spend, and the time is 12 ~ 48 h.
Preferably, the bonderite described in S2 for sodium hypophosphite, sodium dihydrogen phosphate, disodium hydrogen phosphate it is one or more;
The mass ratio of the nitrogenous graphene hydrogel and bonderite is 1:5~1:10.
Preferably, the temperature of the annealing is 100 ~ 400 DEG C, and annealing time is 1 ~ 4 h, and annealing process heating is fast
Rate is 1 ~ 10 DEG C/min.
Preferably, the binding agent described in S3 is one in Kynoar, polytetrafluoroethylene (PTFE) and sodium carboxymethylcellulose
Kind.
Preferably, the mass ratio of the composite nano materials described in S3, acetylene black and binding agent is 7 ~ 9:0.5~3:0.5~3.
Compared with prior art, advantageous effect of the present invention is:
(1)The present invention, using graphene oxide, source of iron and bonderite as raw material, is made under a cryogenic conditions by itrogenous organic substance
Method for oxidant and the hydro-thermal sum of binding agent double action is successfully prepared for a kind of FeP/ nitrogen, phosphor codoping graphene electricity
Chemistry storage sodium combination electrode, aeroge is in black, very light weight(100 mg)It is a kind of nano-porous materials, there is certain bullet
Property and flexibility.
(2)The present invention is for nitrogen-phosphor codoping graphene in other reports, and pattern is three-dimensional under scanning electron microscope
Layered structure is staggeredly connected, shows very bigger serface between layers.The nanometer Fe P material structures rule of preparation, uniformly
It is steadily supported on graphene layer and interlayer, even size distribution(30~80 nm).
(3)The material FeP/ nitrogen of the present invention, nitrogen and phosphorus element composition is 11.2%, 0.38% in phosphor codoping graphene(It is free of
P elements in FeP), there is presently no the graphene reports for seeing such high nitrogen and phosphorus content.
(4)In the present invention, the FeP that produces is Nano grade, a part equably adsorb on the surface of modified graphene and
Edge, a part are located at graphene between layers, on the one hand such structure avoids the reunion of FeP particles, ensure each
Molecule is adequately reacted, and another aspect nanoscale FeP has big specific surface area, during sodium ion insertion and abjection
More active sites are provided.In addition, in high temperature phosphorization processing procedure, the phosphorus atoms in the hydrogen phosphide of graphene surface are adsorbed
The nitrogen-atoms on graphene can partly be replaced, form the graphene of nitrogen, phosphor codoping, graphene is increased by nitrogen, phosphorus doping
Carbon-coating spacing so as to effectively facilitate sodium ion in the insertion of graphene carbon interlayer and abjection process, and then greatlys improve
The specific discharge capacity of carbon matrix material, while be conducive to the formation that class lacks number of plies graphene.
(5)The method of the present invention both considers how the size of regulation and control FeP particles, while also completes hetero atom in graphene
Doping.The composite nano materials being prepared have more storage sodium active sites, and can provide shorter sodium ion and expand
Channel is dissipated, as the combination electrode that the active material of electrochemistry storage sodium is prepared, helps to enhance its electrochemistry storage sodium
Performance.
(6)Building-up process of the present invention is simple, of low cost, and energy consumption is relatively low, reacts without reaction kettle, compared under low temperature condition
A kind of a kind of FeP/ nitrogen of three-dimensional, phosphor codoping graphene aerogel can be obtained, nano particle can provide short sodium ion diffusion
Channel as the combination electrode that the active material of electrochemistry storage sodium is prepared, shows excellent electrochemistry storage sodium
Can, have and commercially produce potentiality.
Description of the drawings
Fig. 1 is the FeP/ nitrogen prepared in the embodiment of the present invention 1, the X-ray diffractogram of phosphor codoping graphene composite material.
Fig. 2 a are the FeP/ nitrogen prepared in the embodiment of the present invention 1, the scanning electron microscope (SEM) photograph of phosphor codoping graphene composite material,
Fig. 2 b are the FeP/ nitrogen prepared in embodiment 1, the pictorial diagram of phosphor codoping graphene composite material.
Fig. 3 is the FeP/ nitrogen prepared in the embodiment of the present invention 1, the x-ray photoelectron spectroscopy of phosphor codoping graphene composite material
Figure.
Fig. 4 is the FeP/ nitrogen prepared in the embodiment of the present invention 1, phosphor codoping graphene composite material as sodium-ion battery
The constant current charge-discharge performance map of negative material.
Fig. 5 is first three weeks charging and discharging curve figure of the 4 gained sample of the embodiment of the present invention under 50 mAh/ g current densities.
Fig. 6 is scanning electron microscope (SEM) figure of 5 gained sample of the embodiment of the present invention.
Fig. 7 is first three weeks charging and discharging curve of the 5 gained sample of the embodiment of the present invention under 50 mAh/ g current densities
Figure.
Fig. 8 is cycle performance curve graph of the 5 gained sample of the embodiment of the present invention under 50 mAh/ g current densities.
Fig. 9 is first three weeks charging and discharging curve figure of the 6 gained sample of the embodiment of the present invention under 50 mAh/ g current densities.
Figure 10 is first three weeks charging and discharging curve of the 7 gained sample of the embodiment of the present invention under 50 mAh/ g current densities
Figure.
Figure 11 is first three weeks charging and discharging curve figure of the 8 gained sample of the embodiment of the present invention under 50 mAh/ g current densities.
Specific embodiment
Embodiment 1:
The preparation method of a kind of FeP/ nitrogen, phosphor codoping graphene electrochemistry storage sodium combination electrode, includes the following steps:
S1. graphene oxide is dispersed in water, graphene oxide solution, the concentration of graphene oxide solution is obtained after ultrasound
About 15g/ ml.
S2. a certain amount of Iron(III) chloride hexahydrate, Iron(III) chloride hexahydrate and stone are added into the graphene liquid that S1 is obtained
The mass ratio of black alkene is 2:1;Add ethylenediamine ultrasound mixing, the molar ratio of ethylenediamine and graphene is 2:1, it is anti-to carry out hydro-thermal
Should, hydrothermal temperature is 90 DEG C, heats 10 h, and freeze-drying process is carried out after natural cooling, and the temperature of freeze-drying is -50 DEG C,
Time is 12 h, obtains nitrogenous graphene hydrogel;Add in bonderite sodium hypophosphite, nitrogenous graphene hydrogel and time phosphorous
The mass ratio of sour sodium is 1:10, it is placed in tube furnace, then made annealing treatment in nitrogen or argon gas atmosphere, annealing temperature is
200 DEG C, annealing time is 2 h, and annealing process heating rate is 5 DEG C/min.
S3. sodium active material is stored up using the composite nano materials that S2 is obtained as electrochemistry, with acetylene black, carboxymethyl cellulose
Plain sodium is sufficiently mixed under stiring, is tuned into uniform slurry, which is equably coated onto on the copper foil as collector, is done
Dry, rolling obtains electrode, and the component and its mass percentage content of combination electrode are composite nano materials:Acetylene black:Carboxymethyl
Sodium cellulosate 7 ~ 9:0.5~3:0.5~3.
It can be seen that in FeP/ nitrogen, phosphor codoping graphene nanocomposite material the position of each diffraction maximums of FeP and relatively strong in Fig. 1
Degree matches with JCPDS (Joint Committee on Powder Diffraction Standards) card (65-2595).
Spherical FeP homoepitaxials be can be seen that in Fig. 2 a on few layer graphene surface, the granular size of FeP is 30 ~ 80 nm,
Black is presented in gel pictorial diagram in Fig. 2 b, and surface folding is porous.
In Fig. 3 XPS find out in graphene composite material there are C-P and C-N key texts graphene successfully adulterate nitrogen phosphorus
Element, in the graphene nitrogen and phosphorus element composition be 11.2% (atomic ratio, similarly hereinafter), 0.38%(Without the P elements in FeP).
Electrochemical results are shown in Fig. 4:During with 50 mA/ g constant-current discharges, FeP/ nitrogen, phosphor codoping graphene are answered
The electrochemistry of composite electrode stores up the initial reversible capacity of sodium as 1625 mAh/ g, and reversible capacity is 570 mAh/ g after 50 cycles, is shown
High specific capacity and excellent stable circulation performance are shown.
Embodiment 2:
Graphene aqueous solution is obtained by the method in above-described embodiment 1, adds a certain amount of Iron(III) chloride hexahydrate, six hydration trichlorines
The mass ratio for changing iron and graphene is 1:1;Add ethylenediamine ultrasound mixing, the molar ratio of ethylenediamine and graphene is 1:1, into
Row hydro-thermal reaction, hydrothermal temperature are 60 DEG C, heat 10 h, freeze-drying process, the temperature of freeze-drying are carried out after natural cooling
It it is -20 DEG C, the time is 48 h, obtains nitrogenous graphene hydrogel;Then, bonderite sodium hypophosphite is added in, is placed in tube furnace
In, the mass ratio of nitrogenous graphene hydrogel and sodium hypophosphite is 1:5, then carried out at annealing in nitrogen or argon gas atmosphere
Reason, annealing temperature are 100 DEG C, and annealing time is 4 h, and annealing process heating rate is 1 DEG C/min, other are obtained such as embodiment 1
A kind of FeP/ nitrogen, the phosphor codoping graphene black aeroge arrived, the granular size of FeP is 20 ~ 100 nm.
Embodiment 3:
Graphene aqueous solution is obtained by the method in above-described embodiment 1, adds a certain amount of frerrous chloride, frerrous chloride and graphene
Mass ratio be 4:1;Add ammonium hydroxide ultrasound mixing, the molar ratio of ammonium hydroxide and graphene is 2:1, carry out hydro-thermal reaction, hydro-thermal
Temperature is 90 DEG C, heats 20 h, and freeze-drying process is carried out after natural cooling, and the temperature of freeze-drying is -30 DEG C, the time 24
H obtains nitrogenous graphene hydrogel;Then, bonderite disodium hydrogen phosphate, nitrogenous graphene hydrogel and disodium hydrogen phosphate are added in
Mass ratio be 1:10, it is placed in tube furnace, then made annealing treatment in nitrogen or argon gas atmosphere, annealing temperature is 400 DEG C,
Annealing time is 1 h, and annealing process heating rate is 10 DEG C/min, other are such as embodiment 1, obtained a kind of FeP/ nitrogen, phosphorus
Codope graphene black aeroge, the granular size of FeP is 80 ~ 130 nm.
Embodiment 4:
Source of iron in embodiment 1 is changed to six nitric hydrate iron, other are such as embodiment 1, during with 50 mA/ g constant-current discharges,
The results are shown in Figure 5 for first three weeks charge-discharge test.The charge/discharge capacity of first three weeks is respectively 710/1657,660/705,644/
682 mA/ g。
Embodiment 5:
Itrogenous organic substance in embodiment 1 is changed to melamine, other are such as embodiment 1, scanning electron microscope (SEM) photograph shown in fig. 6
Display FeP nano particles dispersion is grown on nitrogen, on phosphor codoping graphene, and FeP granular sizes are 60-120 nm.With 50 mA/
During g constant-current discharges, first three weeks, charge-discharge test result was as shown in Fig. 7.3 periods before gained FeP/ nitrogen, phosphor codoping graphene
Discharge capacity maintain more than 600 mAh/ g, as shown in Figure 7.After recycling 50 weeks, specific capacity is 550 mAh/ g, tentatively
Good chemical property is shown, as shown in Fig. 8.
Embodiment 6:
Sodium carboxymethylcellulose in embodiment 1 is changed to Kynoar, other are put such as embodiment 1 with 50mA/ g constant currents
When electric, the results are shown in Figure 9 for first three weeks charge-discharge test.The charge/discharge capacity of first three weeks is respectively 310/1030,281/343,
272/324 mA/ g。
Embodiment 7:
Sodium carboxymethylcellulose in embodiment 1 is changed to polytetrafluoroethylene (PTFE), other are put such as embodiment 1 with 50mA/ g constant currents
When electric, the results are shown in Figure 10 for first three weeks charge-discharge test.The charge/discharge capacity of first three weeks is respectively 355/840,317/359,
299/325 mA/ g。
Embodiment 8:
Sodium hypophosphite in embodiment 1 is changed to sodium dihydrogen phosphate, other are such as embodiment 1, during with 50mA/ g constant-current discharges,
First three weeks charge-discharge test result is as shown in figure 11.The charge/discharge capacity of first three weeks is respectively 708/940,653/708,643/
682 mA/ g。
The embodiment is the preferred embodiments of the present invention, but present invention is not limited to the embodiments described above, not
Away from the present invention substantive content in the case of, those skilled in the art can make it is any it is conspicuously improved, replace
Or modification all belongs to the scope of protection of the present invention.
Claims (10)
1. a kind of FeP/ nitrogen, phosphor codoping graphene electrochemistry store up sodium combination electrode, which is characterized in that the combination electrode has
The redox graphene black gel of three-dimensional structure, graphene surface In-situ reaction have FeP particles;The FeP nanometers
Grain uniformity, grain size are 30 ~ 80 nm;The graphene is modified graphene, surface and interlayer doped with nitrogen, phosphorus atoms.
2. a kind of FeP/ nitrogen, phosphor codoping graphene electrochemistry store up the preparation method of sodium combination electrode, which is characterized in that including such as
Lower step:
S1. graphene oxide is dispersed in water, graphene oxide solution is obtained after ultrasound;
S2. a certain amount of source of iron is added into the graphene oxide solution that S1 is obtained, adds in organic compounds containing nitrogen ultrasound mixing,
Hydro-thermal reaction is carried out, freeze-drying process is carried out after natural cooling, obtains nitrogenous graphene hydrogel;Then, bonderite is added in,
It is placed in tube furnace, is passed through nitrogen or argon gas is made annealing treatment, obtain composite nano materials;
S3. sodium active material is stored up using the composite nano materials described in S2 as electrochemistry, is mixed with acetylene black, binding agent,
Uniform slurry is tuned into, is applied on the copper foil as collector, dry, rolling obtains FeP/ nitrogen, phosphor codoping graphene electricity
Chemistry storage sodium combination electrode.
3. a kind of FeP/ nitrogen according to claim 2, phosphor codoping graphene electrochemistry store up the preparation side of sodium combination electrode
Method, which is characterized in that a concentration of 15 g/ml of the graphene oxide described in S1.
4. a kind of FeP/ nitrogen according to claim 2, phosphor codoping graphene electrochemistry store up the preparation side of sodium combination electrode
Method, which is characterized in that the mass ratio of source of iron and graphene described in S2 is 1:1~4:1, organic compounds containing nitrogen and graphene
Molar ratio is 1:1~2:1.
5. a kind of FeP/ nitrogen according to claim 2, phosphor codoping graphene electrochemistry store up the preparation side of sodium combination electrode
Method, which is characterized in that the source of iron described in S2 is frerrous chloride, Iron(III) chloride hexahydrate, six nitric hydrate iron and their knot
It is one or more in brilliant hydrate.
6. a kind of FeP/ nitrogen according to claim 2, phosphor codoping graphene electrochemistry store up the preparation side of sodium combination electrode
Method, which is characterized in that organic compounds containing nitrogen described in S2 is ethylenediamine, melamine, ammonium hydroxide are therein one or more.
7. a kind of FeP/ nitrogen according to claim 2, phosphor codoping graphene electrochemistry store up the preparation side of sodium combination electrode
Method, which is characterized in that the hydrothermal temperature described in S2 is 60 DEG C ~ 90 DEG C, and the time is 10 ~ 20 h;The freeze-drying temperature
It it is -50 ~ -20 DEG C, sublimation drying is 12 ~ 48 h.
8. a kind of FeP/ nitrogen according to claim 2, phosphor codoping graphene electrochemistry store up the preparation side of sodium combination electrode
Method, which is characterized in that nitrogenous graphene hydrogel described in S2 is 1 in mass ratio with bonderite:5~1:10;The annealing
Temperature is 100 ~ 400 DEG C, and annealing time is 1 ~ 4 h, and annealing process heating rate is 1 ~ 10 DEG C/min;The bonderite is secondary
Sodium phosphite, sodium dihydrogen phosphate, disodium hydrogen phosphate it is one or more.
9. a kind of FeP/ nitrogen according to claim 2, phosphor codoping graphene electrochemistry store up the preparation side of sodium combination electrode
Method, which is characterized in that the binding agent described in S3 is one kind in Kynoar, polytetrafluoroethylene (PTFE) and sodium carboxymethylcellulose.
10. a kind of FeP/ nitrogen according to claim 2, phosphor codoping graphene electrochemistry store up the preparation side of sodium combination electrode
Method, which is characterized in that the mass ratio of composite nano materials, acetylene black and binding agent described in S3 is 7 ~ 9:0.5~3:0.5~3.
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CN114574890A (en) * | 2022-03-19 | 2022-06-03 | 南昌大学 | Self-formed phosphorus-doped redox graphene aerogel catalyst and preparation method and application thereof |
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