CN111740105A - S, N co-doped porous graphene modified copper phosphide lithium ion battery negative electrode material - Google Patents
S, N co-doped porous graphene modified copper phosphide lithium ion battery negative electrode material Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion batteries, and discloses an S, N co-doped porous graphene modified copper phosphide lithium ion battery cathode material, wherein N atoms are doped with graphene to manufacture structural defects and reduce the accumulation of graphene, sodium dodecyl benzene sulfonate is used as an S source to obtain S, N co-doped porous graphene, the surface of the S, N co-doped porous graphene is highly curved, a S, N doped graphene sheet layer is used for constructing a three-dimensional porous net structure, the three-dimensional porous net structure has lower charge transfer resistance and faster reaction kinetics, copper sulfate is used as a copper source to obtain S, N co-doped porous graphene modified uniformly distributed nano cuprous oxide hollow spheres, and the hollow spheres are phosphorized by using sodium phosphate to obtain S, N co-doped porous graphene modified copper phosphide, wherein the copper phosphide has a nano hollow sphere shape and a regular sheet structure, so that the volume expansion and agglomeration of copper phosphide are effectively relieved, and the chemical stability of an electrode is improved, the charge and discharge capacity of the electrode material is improved, so that the electrode material has excellent cycling stability and rate capability.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an S, N co-doped porous graphene modified copper phosphide lithium ion battery cathode material.
Background
The electrochemical energy storage device has the advantages of high efficiency and low pollution, is greatly concerned by all countries in the world, wherein the most widely used rechargeable lithium ion battery is applied to the fields of electronic products, electric automobiles and the like, graphite is a cathode material which is most widely applied, but the graphite has great limitation, the lithium ion intercalation potential is close to that of metal lithium, danger is easy to occur, and meanwhile, the theoretical specific capacity of the graphite is low, so that the requirement of people on endurance capacity is difficult to meet.
Transition metal phosphide has higher theoretical specific capacity, lower polarization and lower voltage platform, and the theoretical specific capacity of copper phosphide is particularly outstanding and becomes a research hotspot in recent years, but in the charging and discharging process, copper phosphide can expand in volume and agglomerate, so that the circulation capacity is poorer, the rate capability is not good, and the large-scale application of copper phosphide is seriously hindered, and graphene has good conductivity, larger specific surface area and better structural stability, and can effectively accelerate the transfer of electrons after being compounded with copper phosphide to provide buffer for the volume change of copper phosphide, so that the problem is solved by adopting a mode of modifying copper phosphide by using S, N codoped porous graphene.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides an S, N co-doped porous graphene modified copper phosphide lithium ion battery cathode material, and solves the problems of poor cycling stability and poor rate capability of the copper phosphide cathode material.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the S, N co-doped porous graphene modified copper phosphide lithium ion battery negative electrode material is prepared by the following method:
(1) adding urea into a crucible, covering a cover, placing the crucible in a muffle furnace, calcining for 3-5h at the temperature of 520-;
(2) adding deionized water, a dispersant polyvinyl alcohol, a phase inversion agent tetrabutylammonium bromide and sodium dodecyl benzene sulfonate into a three-neck flask, adding ground nano powdery N-doped porous graphene, performing ultrasonic dispersion for 40-80min, continuing mechanical stirring, performing condensation reflux for 2-4h at 90-110 ℃, filtering, washing and drying, placing a product obtained by drying in an atmosphere tube furnace, and sintering for 1-3h at 600-700 ℃ in the nitrogen atmosphere to obtain S, N co-doped porous graphene;
(3) adding deionized water, ethylene glycol and S, N codoped porous graphene into a beaker, performing ultrasonic treatment for 40-80min to disperse uniformly, adding concentrated ammonia water, copper sulfate and a template agent sodium dodecyl sulfate, controlling the volume ratio of the concentrated ammonia water to the deionized water to be 5-10:100, performing ultrasonic treatment for 10-20min to disperse uniformly, adding a reducing agent ascorbic acid, performing ultrasonic treatment for 20-40min to disperse uniformly, centrifuging, washing and drying to obtain a S, N codoped porous graphene modified cuprous oxide hollow sphere;
(4) grinding S, N co-doped porous graphene modified cuprous oxide hollow spheres into powder, placing the powder on one side of a porcelain boat, placing sodium phosphate on the other side of the porcelain boat, placing the porcelain boat in an atmosphere tube furnace, performing heat treatment at 270-330 ℃ for 1-3h in a nitrogen atmosphere, and cooling to obtain the S, N co-doped porous graphene modified copper phosphide lithium ion battery cathode material.
Preferably, the atmosphere tube furnace in step (1) includes the main part, and the bottom swing joint of main part has the base, and the top swing joint of base has the motor, and the left side swing joint of motor has the action wheel, and the centre swing joint of main part has the boiler tube, and the right side swing joint of boiler tube has the gas pocket, and the right side swing joint of boiler tube has the bearing, and the centre swing joint of boiler tube has the follower, and the inside swing joint of boiler tube has the container, and the bottom swing joint of container has the universal wheel.
Preferably, the mass ratio of the polyvinyl alcohol, the tetrabutylammonium bromide, the sodium dodecyl benzene sulfonate and the N-doped porous graphene in the step (2) is 200-400:20-40:80-120: 100.
Preferably, the mass ratio of the S, N co-doped porous graphene, copper sulfate, sodium dodecyl sulfate and ascorbic acid in the step (3) is 5-30:100:400-800: 300-600.
Preferably, the mass ratio of the S, N co-doped porous graphene-modified cuprous oxide hollow spheres to the sodium phosphate in the step (4) is 100: 5-10.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the S, N co-doped porous graphene modified copper phosphide lithium ion battery cathode material, graphitized carbon nitride powder is used as a template agent, methane is used as a carbon source, N-doped porous graphene is obtained through roasting, structural defects are made, the specific surface area is increased, the stacking of graphene is reduced, the charge density of adjacent carbon atoms is improved, more lithium storage active sites are provided, the electrochemical lithium storage performance is enhanced, polyvinyl alcohol is used as a dispersing agent, tetrabutylammonium bromide is used as a phase conversion agent, sodium dodecylbenzene sulfonate is used as a bonding agent, sulfonic groups in the sodium dodecylbenzene sulfonate react with oxygen-containing functional groups in graphene, S, N co-doped porous graphene is obtained through sintering, the surface of graphene is highly bent due to the doping of S atoms, the specific surface area is greatly increased, the active sites on the surface of graphene are further improved, a S, N doped graphene sheet layer constructs a three-dimensional porous network structure, the graphene material has lower charge transfer resistance and faster reaction kinetics, accelerates the transmission of electrons, enhances the conductivity of graphene, and simultaneously improves the ion adsorption and diffusion degrees of the surface of the graphene.
The S, N codoped porous graphene modified copper phosphide lithium ion battery cathode material is prepared by taking copper sulfate as a copper source, sodium dodecyl sulfate as a template agent and ascorbic acid as a reducing agent, so that S, N codoped porous graphene modified cuprous oxide hollow spheres are obtained, the cuprous oxide hollow spheres are uniformly distributed on the surface of graphene, are uniformly distributed in shape, reduce agglomeration, increase the specific surface area, and are phosphated by sodium phosphate to obtain S, N codoped porous graphene modified copper phosphide, wherein the copper phosphide has the shape of the hollow spheres, so that the specific surface area and the pore structure are further improved, the electron transmission and lithium ion diffusion are facilitated, meanwhile, the electrode material is uniformly distributed and has a regular lamellar structure, the volume expansion and agglomeration of the copper phosphide in the charging and discharging process are effectively relieved, the chemical stability of an electrode is improved, and the transfer resistance and diffusion resistance of charges are reduced at the same time, the conductivity is increased, and the charge and discharge capacity of the electrode material is improved, so that the electrode material has excellent cycle stability and rate capability.
Drawings
FIG. 1 is a schematic sectional elevational view of an atmospheric tube furnace;
FIG. 2 is a schematic view of the inner structure of the furnace tube.
1. A main body; 2. a base; 3. a motor; 4. a driving wheel; 5. a furnace tube; 6. air holes; 7. a bearing; 8. a driven wheel; 9. a container; 10. a universal wheel.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: the S, N co-doped porous graphene modified copper phosphide lithium ion battery negative electrode material is prepared by the following method:
(1) adding urea into a crucible, covering a cover, placing the crucible in a muffle furnace, calcining for 3-5h at the temperature of 520-580 ℃, cooling, grinding by using a mortar to obtain template graphitized carbon nitride powder, placing a template in a porcelain boat in an atmosphere tube furnace, wherein the atmosphere tube furnace comprises a main body, the bottom of the main body is movably connected with a base, the top of the base is movably connected with a motor, the left side of the motor is movably connected with a driving wheel, the middle of the main body is movably connected with a furnace tube, the right side of the furnace tube is movably connected with an air hole, the right side of the furnace tube is movably connected with a bearing, the middle of the furnace tube is movably connected with a driven wheel, the interior of the furnace tube is movably connected with a container, the bottom of the container is movably connected with a universal wheel, the volume ratio of the two is 85-95:5-15 under the atmosphere of mixed, stopping introducing methane gas, heating to 820-880 ℃ in the atmosphere of mixed gas of argon and hydrogen, roasting for 40-80min, and cooling to obtain N-doped porous graphene;
(2) adding deionized water, a dispersant polyvinyl alcohol, a phase inversion agent tetrabutylammonium bromide and sodium dodecyl benzene sulfonate into a three-neck flask, then adding ground nano powdery N-doped porous graphene, wherein the mass ratio of the polyvinyl alcohol to the tetrabutylammonium bromide to the sodium dodecyl benzene sulfonate to the N-doped porous graphene is 200-80-20: 80-120:100, uniformly dispersing by ultrasonic treatment for 40-80min, continuously mechanically stirring, carrying out condensation reflux for 2-4h at 90-110 ℃, filtering, washing and drying, placing a dried product into an atmosphere tube furnace, and sintering for 1-3h at 600-700 ℃ in a nitrogen atmosphere to obtain S, N co-doped porous graphene;
(3) adding deionized water, ethylene glycol and S, N co-doped porous graphene into a beaker, performing ultrasonic treatment for 40-80min to disperse uniformly, adding concentrated ammonia water, copper sulfate and a template agent sodium dodecyl sulfate, controlling the volume ratio of the concentrated ammonia water to the deionized water to be 5-10:100, performing ultrasonic treatment for 10-20min to disperse uniformly, adding a reducing agent ascorbic acid, wherein the mass ratio of S, N co-doped porous graphene, copper sulfate, sodium dodecyl sulfate and ascorbic acid is 5-30:100:400-800:300-600, performing ultrasonic treatment for 20-40min to disperse uniformly, centrifuging, washing and drying to obtain a S, N co-doped porous graphene modified cuprous oxide hollow sphere;
(4) grinding S, N co-doped porous graphene modified cuprous oxide hollow spheres into powder, placing the powder on one side of a porcelain boat, placing sodium phosphate on the other side of the porcelain boat with the mass ratio of 100:5-10, placing the porcelain boat in an atmosphere tube furnace, performing heat treatment at 270-330 ℃ for 1-3h in a nitrogen atmosphere, and cooling to obtain the S, N co-doped porous graphene modified copper phosphide lithium ion battery cathode material.
Example 1
(1) Adding urea into a crucible, covering a cover, placing the crucible in a muffle furnace, calcining for 3 hours at 520 ℃, cooling, grinding by using a mortar to obtain template graphitized carbon nitride powder, placing the template in a porcelain boat in an atmosphere tube furnace, wherein the atmosphere tube furnace comprises a main body, the bottom of the main body is movably connected with a base, the top of the base is movably connected with a motor, the left side of the motor is movably connected with a driving wheel, the middle of the main body is movably connected with a furnace tube, the right side of the furnace tube is movably connected with an air hole, the right side of the furnace tube is movably connected with a bearing, the middle of the furnace tube is movably connected with a driven wheel, the interior of the furnace tube is movably connected with a container, the bottom of the container is movably connected with a universal wheel, the volume ratio of the two is 85:15 under the atmosphere of argon and hydrogen mixed gas, introducing methane for 1 hour at 470 ℃, stopping introducing methane gas, heating, cooling to obtain N-doped porous graphene;
(2) adding deionized water, a dispersant polyvinyl alcohol, a phase inversion agent tetrabutylammonium bromide and sodium dodecyl benzene sulfonate into a three-neck flask, adding ground nano powdery N-doped porous graphene, wherein the mass ratio of the polyvinyl alcohol to the tetrabutylammonium bromide to the sodium dodecyl benzene sulfonate to the N-doped porous graphene is 200:20:80:100, performing ultrasonic treatment for 40min to disperse uniformly, continuing to perform mechanical stirring, performing condensation reflux for 2h at 90 ℃, filtering, washing and drying, placing a product obtained by drying into an atmosphere tubular furnace, and sintering for 1h at 600 ℃ in a nitrogen atmosphere to obtain S, N co-doped porous graphene;
(3) adding deionized water, ethylene glycol and S, N codoped porous graphene into a beaker, performing ultrasonic treatment for 40min to disperse uniformly, adding concentrated ammonia water, copper sulfate and a template agent sodium dodecyl sulfate, controlling the volume ratio of the concentrated ammonia water to the deionized water to be 5:100, performing ultrasonic treatment for 10min to disperse uniformly, adding a reducing agent ascorbic acid, wherein the mass ratio of S, N codoped porous graphene, copper sulfate, sodium dodecyl sulfate and ascorbic acid is 5:100:400:300, performing ultrasonic treatment for 20min to disperse uniformly, centrifuging, washing and drying to obtain a S, N codoped porous graphene modified cuprous oxide hollow sphere;
(4) grinding S, N co-doped porous graphene modified cuprous oxide hollow spheres into powder, placing the powder on one side of a porcelain boat, placing sodium phosphate on the other side of the porcelain boat with the mass ratio of 100:5, placing the porcelain boat in an atmosphere tube furnace, performing heat treatment at 270 ℃ for 1h in a nitrogen atmosphere, and cooling to obtain the S, N co-doped porous graphene modified copper phosphide lithium ion battery cathode material.
Example 2
(1) Adding urea into a crucible, covering a cover, placing the crucible in a muffle furnace, calcining for 4 hours at 550 ℃, grinding by using a mortar after cooling to obtain template graphitized carbon nitride powder, placing the template in a porcelain boat in an atmosphere tube furnace, wherein the atmosphere tube furnace comprises a main body, the bottom of the main body is movably connected with a base, the top of the base is movably connected with a motor, the left side of the motor is movably connected with a driving wheel, the middle of the main body is movably connected with a furnace tube, the right side of the furnace tube is movably connected with an air hole, the right side of the furnace tube is movably connected with a bearing, the middle of the furnace tube is movably connected with a driven wheel, the interior of the furnace tube is movably connected with a container, the bottom of the container is movably connected with a universal wheel, the volume ratio of the two is 90:10 under the atmosphere of mixed gas of argon and hydrogen, introducing methane for 2 hours at 500 ℃, stopping introducing methane gas, cooling to obtain N-doped porous graphene;
(2) adding deionized water, a dispersant polyvinyl alcohol, a phase inversion agent tetrabutylammonium bromide and sodium dodecyl benzene sulfonate into a three-neck flask, adding ground nano powdery N-doped porous graphene, wherein the mass ratio of the polyvinyl alcohol to the tetrabutylammonium bromide to the sodium dodecyl benzene sulfonate to the N-doped porous graphene is 300:30:100:100, performing ultrasonic treatment for 60min to disperse uniformly, continuing to perform mechanical stirring, performing condensation reflux for 3h at 100 ℃, filtering, washing and drying, placing a product obtained by drying into an atmosphere tubular furnace, and sintering for 2h at 650 ℃ in a nitrogen atmosphere to obtain S, N co-doped porous graphene;
(3) adding deionized water, ethylene glycol and S, N codoped porous graphene into a beaker, performing ultrasonic treatment for 60min to disperse uniformly, adding concentrated ammonia water, copper sulfate and a template agent sodium dodecyl sulfate, controlling the volume ratio of the concentrated ammonia water to the deionized water to be 7.5:100, performing ultrasonic treatment for 15min to disperse uniformly, adding a reducing agent ascorbic acid, wherein the mass ratio of S, N codoped porous graphene, copper sulfate, sodium dodecyl sulfate and ascorbic acid is 17.5:100:600:450, performing ultrasonic treatment for 30min to disperse uniformly, centrifuging, washing and drying to obtain S, N codoped porous graphene modified cuprous oxide hollow spheres;
(4) grinding S, N co-doped porous graphene modified cuprous oxide hollow spheres into powder, placing the powder on one side of a porcelain boat, placing sodium phosphate on the other side of the porcelain boat with the mass ratio of 100:7.5, placing the porcelain boat in an atmosphere tube furnace, carrying out heat treatment for 2h at 300 ℃ in a nitrogen atmosphere, and cooling to obtain the S, N co-doped porous graphene modified copper phosphide lithium ion battery cathode material.
Example 3
(1) Adding urea into a crucible, covering a cover, placing the crucible in a muffle furnace, calcining for 3 hours at 540 ℃, grinding by using a mortar after cooling to obtain template graphitized carbon nitride powder, placing the template in a porcelain boat in an atmosphere tube furnace, wherein the atmosphere tube furnace comprises a main body, the bottom of the main body is movably connected with a base, the top of the base is movably connected with a motor, the left side of the motor is movably connected with a driving wheel, the middle of the main body is movably connected with a furnace tube, the right side of the furnace tube is movably connected with an air hole, the right side of the furnace tube is movably connected with a bearing, the middle of the furnace tube is movably connected with a driven wheel, the interior of the furnace tube is movably connected with a container, the bottom of the container is movably connected with a universal wheel, under the atmosphere of mixed gas of argon and hydrogen, the volume ratio of the two is 89:11, introducing methane for 2 hours at 490 ℃, stopping introducing methane gas, cooling to obtain N-doped porous graphene;
(2) adding deionized water, a dispersant polyvinyl alcohol, a phase inversion agent tetrabutylammonium bromide and sodium dodecyl benzene sulfonate into a three-neck flask, adding ground nano powdery N-doped porous graphene, wherein the mass ratio of the polyvinyl alcohol to the tetrabutylammonium bromide to the sodium dodecyl benzene sulfonate to the N-doped porous graphene is 280:35:110:100, performing ultrasonic treatment for 50min to disperse uniformly, continuing to perform mechanical stirring, performing condensation reflux for 4h at 90 ℃, filtering, washing and drying, placing a product obtained by drying into an atmosphere tubular furnace, and sintering for 1h at 600 ℃ in a nitrogen atmosphere to obtain S, N co-doped porous graphene;
(3) adding deionized water, ethylene glycol and S, N codoped porous graphene into a beaker, performing ultrasonic treatment for 40min to disperse uniformly, adding concentrated ammonia water, copper sulfate and a template agent sodium dodecyl sulfate, controlling the volume ratio of the concentrated ammonia water to the deionized water to be 8:100, performing ultrasonic treatment for 20min to disperse uniformly, adding a reducing agent ascorbic acid, wherein the mass ratio of S, N codoped porous graphene, copper sulfate, sodium dodecyl sulfate and ascorbic acid is 25:100:400:600, performing ultrasonic treatment for 20min to disperse uniformly, centrifuging, washing and drying to obtain a S, N codoped porous graphene modified cuprous oxide hollow sphere;
(4) grinding S, N co-doped porous graphene modified cuprous oxide hollow spheres into powder, placing the powder on one side of a porcelain boat, placing sodium phosphate on the other side of the porcelain boat with the mass ratio of 100:6, placing the porcelain boat in an atmosphere tube furnace, performing heat treatment at 330 ℃ for 1h in a nitrogen atmosphere, and cooling to obtain the S, N co-doped porous graphene modified copper phosphide lithium ion battery cathode material.
Example 4
(1) Adding urea into a crucible, covering a cover, placing the crucible in a muffle furnace, calcining for 5 hours at 580 ℃, cooling, grinding by using a mortar to obtain template graphitized carbon nitride powder, placing the template in a porcelain boat in an atmosphere tube furnace, wherein the atmosphere tube furnace comprises a main body, the bottom of the main body is movably connected with a base, the top of the base is movably connected with a motor, the left side of the motor is movably connected with a driving wheel, the middle of the main body is movably connected with a furnace tube, the right side of the furnace tube is movably connected with an air hole, the right side of the furnace tube is movably connected with a bearing, the middle of the furnace tube is movably connected with a driven wheel, the interior of the furnace tube is movably connected with a container, the bottom of the container is movably connected with a universal wheel, the volume ratio of the two is 95:5 under the atmosphere of mixed gas of argon and hydrogen, introducing methane for 3 hours at 530 ℃, stopping introducing methane gas, cooling to obtain N-doped porous graphene;
(2) adding deionized water, a dispersant polyvinyl alcohol, a phase inversion agent tetrabutylammonium bromide and sodium dodecyl benzene sulfonate into a three-neck flask, adding ground nano powdery N-doped porous graphene, wherein the mass ratio of the polyvinyl alcohol to the tetrabutylammonium bromide to the sodium dodecyl benzene sulfonate to the N-doped porous graphene is 400:40:120:100, performing ultrasonic 80min to disperse uniformly, continuing to mechanically stir, performing condensation reflux for 4 hours at 110 ℃, filtering, washing and drying, placing a product obtained by drying into an atmosphere tube furnace, and sintering for 3 hours at 700 ℃ in a nitrogen atmosphere to obtain S, N co-doped porous graphene;
(3) adding deionized water, ethylene glycol and S, N codoped porous graphene into a beaker, performing ultrasonic treatment for 80min to disperse uniformly, adding concentrated ammonia water, copper sulfate and a template agent sodium dodecyl sulfate, controlling the volume ratio of the concentrated ammonia water to the deionized water to be 10:100, performing ultrasonic treatment for 20min to disperse uniformly, adding a reducing agent ascorbic acid, wherein the mass ratio of S, N codoped porous graphene, copper sulfate, sodium dodecyl sulfate and ascorbic acid is 30:100:800:600, performing ultrasonic treatment for 40min to disperse uniformly, centrifuging, washing and drying to obtain a S, N codoped porous graphene modified cuprous oxide hollow sphere;
(4) grinding S, N co-doped porous graphene modified cuprous oxide hollow spheres into powder, placing the powder on one side of a porcelain boat, placing sodium phosphate on the other side of the porcelain boat with the mass ratio of 100:10, placing the porcelain boat in an atmosphere tube furnace, performing heat treatment at 330 ℃ for 3 hours in a nitrogen atmosphere, and cooling to obtain the S, N co-doped porous graphene modified copper phosphide lithium ion battery cathode material.
Comparative example 1
(1) Adding urea into a crucible, covering a cover, placing the crucible in a muffle furnace, calcining for 3 hours at 500 ℃, grinding by using a mortar after cooling to obtain template graphitized carbon nitride powder, placing the template in a porcelain boat in an atmosphere tube furnace, wherein the atmosphere tube furnace comprises a main body, the bottom of the main body is movably connected with a base, the top of the base is movably connected with a motor, the left side of the motor is movably connected with a driving wheel, the middle of the main body is movably connected with a furnace tube, the right side of the furnace tube is movably connected with an air hole, the right side of the furnace tube is movably connected with a bearing, the middle of the furnace tube is movably connected with a driven wheel, the interior of the furnace tube is movably connected with a container, the bottom of the container is movably connected with a universal wheel, the volume ratio of the two is 80:20 under the atmosphere of mixed gas of argon and hydrogen, introducing methane for 4 hours at 460 ℃, stopping introducing methane gas, cooling to obtain N-doped porous graphene;
(2) adding deionized water, a dispersant polyvinyl alcohol, a phase inversion agent tetrabutylammonium bromide and sodium dodecyl benzene sulfonate into a three-neck flask, adding ground nano powdery N-doped porous graphene, wherein the mass ratio of the polyvinyl alcohol to the tetrabutylammonium bromide to the sodium dodecyl benzene sulfonate to the N-doped porous graphene is 200:20:80:100, performing ultrasonic treatment for 30min to disperse uniformly, continuing to mechanically stir, performing condensation reflux for 2h at 120 ℃, filtering, washing and drying, placing a dried product into an atmosphere tube furnace, and sintering for 1h at 800 ℃ in a nitrogen atmosphere to obtain S, N co-doped porous graphene;
(3) adding deionized water, ethylene glycol and S, N codoped porous graphene into a beaker, performing ultrasonic treatment for 30min to disperse uniformly, adding concentrated ammonia water, copper sulfate and a template agent sodium dodecyl sulfate, controlling the volume ratio of the concentrated ammonia water to the deionized water to be 5:100, performing ultrasonic treatment for 10min to disperse uniformly, adding a reducing agent ascorbic acid, wherein the mass ratio of S, N codoped porous graphene, copper sulfate, sodium dodecyl sulfate and ascorbic acid is 5:100:400:300, performing ultrasonic treatment for 10min to disperse uniformly, centrifuging, washing and drying to obtain a S, N codoped porous graphene modified cuprous oxide hollow sphere;
(4) grinding S, N co-doped porous graphene modified cuprous oxide hollow spheres into powder, placing the powder on one side of a porcelain boat, placing sodium phosphate on the other side of the porcelain boat at a mass ratio of 100:15, placing the porcelain boat in an atmosphere tube furnace, performing heat treatment at 240 ℃ for 1h in a nitrogen atmosphere, and cooling to obtain the S, N co-doped porous graphene modified copper phosphide lithium ion battery cathode material.
Adding S, N co-doped porous graphene modified copper phosphide lithium ion battery negative electrode material, acetylene black and polyvinylidene fluoride obtained in the examples and the comparative examples into an N-methyl pyrrolidone solution, wherein the mass ratio of the S, N co-doped porous graphene modified copper phosphide lithium ion battery negative electrode material to the acetylene black to the polyvinylidene fluoride is 7:2:1, uniformly stirring, uniformly coating the mixed solution on two sides of a copper foil, drying the copper foil in an oven at 80 ℃ for 10 hours, preparing a wafer with the diameter of 12mm from the dried copper foil as a working electrode, taking metal lithium as a counter electrode, a polypropylene microporous membrane as a diaphragm, foamed nickel as a filler and 1mol/L electrolyte of LiPF6The solvent is a mixed solution of ethylene carbonate, dimethyl carbonate and diethyl carbonate in a volume ratio of 1:1:1, the mixed solution is assembled into a button cell in a glove box filled with argon, and the test is carried out in a LAND CT2100A type multi-channel cell performance test system with the test standard of GB/T36276-2018.
Claims (5)
1. An S, N co-doped porous graphene modified copper phosphide lithium ion battery negative electrode material is characterized in that: the preparation method of the S, N co-doped porous graphene modified copper phosphide lithium ion battery negative electrode material comprises the following steps:
(1) adding urea into a crucible, covering a cover, placing the crucible in a muffle furnace, calcining for 3-5h at the temperature of 520-;
(2) adding deionized water, a dispersant polyvinyl alcohol, a phase inversion agent tetrabutylammonium bromide and sodium dodecyl benzene sulfonate into a three-neck flask, adding ground nano powdery N-doped porous graphene, performing ultrasonic dispersion for 40-80min, continuing mechanical stirring, performing condensation reflux for 2-4h at 90-110 ℃, filtering, washing and drying, placing a product obtained by drying in an atmosphere tube furnace, and sintering for 1-3h at 600-700 ℃ in the nitrogen atmosphere to obtain S, N co-doped porous graphene;
(3) adding deionized water, ethylene glycol and S, N codoped porous graphene into a beaker, performing ultrasonic treatment for 40-80min to disperse uniformly, adding concentrated ammonia water, copper sulfate and a template agent sodium dodecyl sulfate, controlling the volume ratio of the concentrated ammonia water to the deionized water to be 5-10:100, performing ultrasonic treatment for 10-20min to disperse uniformly, adding a reducing agent ascorbic acid, performing ultrasonic treatment for 20-40min to disperse uniformly, centrifuging, washing and drying to obtain a S, N codoped porous graphene modified cuprous oxide hollow sphere;
(4) grinding S, N co-doped porous graphene modified cuprous oxide hollow spheres into powder, placing the powder on one side of a porcelain boat, placing sodium phosphate on the other side of the porcelain boat, placing the porcelain boat in an atmosphere tube furnace, performing heat treatment at 270-330 ℃ for 1-3h in a nitrogen atmosphere, and cooling to obtain the S, N co-doped porous graphene modified copper phosphide lithium ion battery cathode material.
2. The S, N co-doped porous graphene modified copper phosphide lithium ion battery negative electrode material of claim 1, wherein: the atmosphere tube furnace in the step (1) comprises a main body, wherein the bottom of the main body is movably connected with a base, the top of the base is movably connected with a motor, the left side of the motor is movably connected with a driving wheel, the middle of the main body is movably connected with a furnace tube, the right side of the furnace tube is movably connected with an air hole, the right side of the furnace tube is movably connected with a bearing, the middle of the furnace tube is movably connected with a driven wheel, the inner part of the furnace tube is movably connected with a container, and the bottom of.
3. The S, N co-doped porous graphene modified copper phosphide lithium ion battery negative electrode material of claim 1, wherein: in the step (2), the mass ratio of the polyvinyl alcohol, the tetrabutylammonium bromide, the sodium dodecyl benzene sulfonate and the N-doped porous graphene is 200-.
4. The S, N co-doped porous graphene modified copper phosphide lithium ion battery negative electrode material of claim 1, wherein: in the step (3), S, N co-doped porous graphene, copper sulfate, sodium dodecyl sulfate and ascorbic acid are mixed in a mass ratio of 5-30:100:400-800: 300-600.
5. The S, N co-doped porous graphene modified copper phosphide lithium ion battery negative electrode material of claim 1, wherein: the mass ratio of the S, N co-doped porous graphene modified cuprous oxide hollow spheres to the sodium phosphate in the step (4) is 100: 5-10.
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