CN113113601B - Hard carbon negative electrode material for lithium ion secondary battery and preparation method thereof - Google Patents
Hard carbon negative electrode material for lithium ion secondary battery and preparation method thereof Download PDFInfo
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- CN113113601B CN113113601B CN202110369511.0A CN202110369511A CN113113601B CN 113113601 B CN113113601 B CN 113113601B CN 202110369511 A CN202110369511 A CN 202110369511A CN 113113601 B CN113113601 B CN 113113601B
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- phosphorus
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- Battery Electrode And Active Subsutance (AREA)
Abstract
A hard carbon negative electrode material for a lithium ion secondary battery and a method for preparing the same, the hard carbon negative electrode material comprising: the hard carbon material comprises a hard carbon precursor, a phosphorus-containing dopant and a polymer, wherein the hard carbon precursor is prepared from a hard carbon raw material, the mass fraction of phosphorus in the phosphorus-containing dopant in the hard carbon negative electrode material is 0.3% -5%, at least one part of the surface of the hard carbon negative electrode material is covered by the polymer, and the mass fraction of the polymer in the hard carbon negative electrode material is 1% -20%. The invention provides a hard carbon negative electrode material for a lithium ion secondary battery and a preparation method thereof, the prepared hard carbon negative electrode material contains 0.3-5% of phosphorus element by mass ratio, phosphorus doping can increase lithium embedding sites of the hard carbon negative electrode material in the charging and discharging process, so that the specific capacity of the hard carbon negative electrode material is improved, the first reversible capacity of the hard carbon negative electrode material is more than 500mAh/g, and the first coulombic efficiency is more than 83%.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a hard carbon negative electrode material for a lithium ion secondary battery and a preparation method thereof.
Background
Lithium ion secondary batteries are widely used in the fields of 3C consumer, power and energy storage batteries due to their advantages of good stability, high energy density, no memory effect, etc. The current commercial lithium ion secondary battery negative electrode material mainly uses a graphite negative electrode as a main material, but the theoretical specific capacity of the graphite negative electrode is lower and is only 372mAh/g, and the large-rate continuous charge and discharge capacity and the low-temperature performance are difficult to effectively improve. Therefore, the development of a new negative electrode material for lithium ion secondary batteries, which has high specific capacity, excellent rate capability and good low-temperature performance, is an important direction of current research.
Disclosure of Invention
In order to solve the above problems, the present invention provides a hard carbon anode material for a lithium ion secondary battery, comprising: the hard carbon material comprises a hard carbon precursor, a phosphorus-containing dopant and a polymer, wherein the hard carbon precursor is prepared from a hard carbon raw material, the mass fraction of phosphorus in the phosphorus-containing dopant in the hard carbon negative electrode material is 0.3% -5%, at least one part of the surface of the hard carbon negative electrode material is covered by the polymer, and the mass fraction of the polymer in the hard carbon negative electrode material is 1% -20%.
Preferably, the hard carbon feedstock comprises one or more of biomass material, high molecular weight polymers, carbon products, and sugars.
Preferably, the biomass material comprises one or more of rice hulls, peanut shells, pistachio shells, walnut shells, sunflower seed shells, pine cones, rice, coconut shells, bamboo, corn cobs, rape straw and bagasse.
Preferably, the high molecular polymer includes one or more of polyvinyl chloride resin, acrylic resin, phenolic resin, epoxy resin, polyester resin, polyamide resin, bismaleimide, polypropylene polycarbonate, polyether ether ketone, and polystyrene.
Preferably, the carbon product comprises one or more of petroleum coke, pitch coke, and coal-based coke.
Preferably, the saccharide includes one or more of fructose, mannose, sucrose, glucose, galactose, galactan, amino sugar, ribose, deoxyribose, starch, cellulose, polysaccharide, pectin, pentose, mannose, mannan, chitin, maltose, gum arabic, glycogen, inulin, and chitin.
Preferably, the phosphorus-containing dopant comprises one or more of phosphorus pentoxide, phosphoric acid, sodium dihydrogen phosphate, sodium phosphate, potassium phosphate, ammonium phosphate and ammonium dihydrogen phosphate.
Preferably, the polymer comprises one or more of polypyrrole, polyaniline, polythiophene and polyimide.
Preferably, the mass ratio of the phosphorus-containing dopant to the hard carbon precursor is (1-20): 100.
the invention also provides a preparation method of the hard carbon negative electrode material for the lithium ion secondary battery, wherein the hard carbon negative electrode material comprises the hard carbon negative electrode material for the lithium ion secondary battery, and the method comprises the following steps:
preparing a hard carbon raw material, a phosphorus-containing dopant and a polymer;
coarsely crushing the hard carbon raw material to obtain coarse crushed materials;
calcining the coarse crushed materials for 1 to 10 hours at the temperature of between 200 and 500 ℃ in an inert gas environment to obtain first calcined materials;
acid cleaning is carried out on the first calcined material by using dilute hydrochloric acid with the mass fraction of less than 15%;
drying, crushing and screening the first calcined material after acid washing in sequence to obtain a hard carbon precursor;
mixing the hard carbon precursor and the phosphorus-containing dopant to obtain a mixture;
calcining the mixture for 2-4 hours at 200-500 ℃ in an inert gas environment to obtain a second calcined material;
dissolving the polymer in water and obtaining a polymer solution;
dissolving the second calcined material into the polymer solution, and stirring to obtain a mixed solution;
drying the mixed solution to obtain a mixed material;
and scattering, screening and demagnetizing the mixture to obtain the hard carbon negative electrode material.
The hard carbon negative electrode material for the lithium ion secondary battery and the preparation method thereof have the advantages that:
(1) The hard carbon negative electrode material prepared by the invention contains 0.3-5% of phosphorus element by mass ratio, and the phosphorus doping can increase lithium insertion sites of the hard carbon negative electrode material in the charging and discharging process, so that the specific capacity of the hard carbon negative electrode material is improved, the first reversible capacity of the hard carbon negative electrode material is more than 500mAh/g, and the first coulombic efficiency is more than 83%;
(2) In the hard carbon cathode material prepared by the invention, the polymer coating can reduce the side reaction of the carbon cathode material and electrolyte, reduce the irreversible lithium ion loss, contribute to providing the stability of SEM and improve the cycle performance;
(3) The raw materials used by the hard carbon cathode material prepared by the invention are low in price, and the preparation process and equipment are mature, so that the hard carbon cathode material is suitable for large-scale production;
(4) When the hard carbon cathode material prepared by the invention is used as a cathode active material of a lithium ion battery, the cycle performance of the battery can be obviously improved, and the capacity retention rate after 2400 cycles at 1C/1C multiplying power is about 89%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is an SEM image of a hard carbon anode material prepared in example 1 of the present invention;
fig. 2 is an SEM image of a hard carbon anode material prepared in example 1 of the present invention;
FIG. 3 is an EDS diagram of a hard carbon anode material prepared in example 1 of the present invention;
fig. 4 is an XRD pattern of the hard carbon anode material prepared in example 1 of the present invention;
fig. 5 is a first charge-discharge curve of a button cell made of the hard carbon negative electrode material prepared in example 1 of the present invention;
fig. 6 is a cycle curve of the hard carbon anode material prepared in example 1 of the present invention at a 1C/1C rate in a pouch cell.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the accompanying drawings in combination with the embodiments. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
The invention provides a hard carbon negative electrode material for a lithium ion secondary battery, which comprises the following components: the hard carbon material comprises a hard carbon precursor, a phosphorus-containing dopant and a polymer, wherein the hard carbon precursor is prepared from a hard carbon raw material, the mass fraction of phosphorus in the phosphorus-containing dopant in the hard carbon negative electrode material is 0.3% -5%, at least one part of the surface of the hard carbon negative electrode material is covered by the polymer, and the mass fraction of the polymer in the hard carbon negative electrode material is 1% -20%.
In embodiments of the present application, the hard carbon feedstock comprises one or more of biomass material, high molecular weight polymers, carbon products, and sugars.
In an embodiment of the present application, the biomass material comprises one or more of rice hulls, peanut shells, pistachio shells, walnut shells, sunflower seed shells, pine cones, rice, coconut shells, bamboo, corn cobs, rape straw, and bagasse.
In an embodiment of the present application, the high molecular polymer includes one or more of polyvinyl chloride resin, acrylic resin, phenolic resin, epoxy resin, polyester resin, polyamide resin, bismaleimide, polypropylene polycarbonate, polyether ether ketone, and polystyrene.
In embodiments herein, the carbon product comprises one or more of petroleum coke, pitch coke, and coal-based coke.
In embodiments of the present application, the saccharide includes one or more of fructose, mannose, sucrose, glucose, galactose, galactan, amino sugar, ribose, deoxyribose, starch, cellulose, polysaccharide, pectin, pentose, mannose, mannan, chitin, maltose, gum arabic, glycogen, inulin, and chitin.
In embodiments of the present application, the phosphorus-containing dopant comprises one or more of phosphorus pentoxide, phosphoric acid, sodium dihydrogen phosphate, sodium phosphate, potassium phosphate, ammonium phosphate, and ammonium dihydrogen phosphate.
In embodiments of the present application, the polymer comprises one or more of polypyrrole, polyaniline, polythiophene, and polyimide.
In the examples of the present application, the mass ratio of the phosphorus-containing dopant to the hard carbon precursor is (1-20): 100.
in an embodiment of the present application, the present invention also provides a method for preparing a hard carbon anode material for a lithium ion secondary battery, the hard carbon anode material comprising the hard carbon anode material for a lithium ion secondary battery as described in any one of the above, the method comprising the steps of:
preparing a hard carbon raw material, a phosphorus-containing dopant and a polymer;
coarsely crushing the hard carbon raw material to obtain coarse crushed materials;
calcining the coarse crushed materials for 1 to 10 hours at the temperature of between 200 and 500 ℃ in an inert gas environment to obtain first calcined materials;
acid cleaning is carried out on the first calcined material by using dilute hydrochloric acid with the mass fraction of less than 15%;
drying, crushing and sieving the first calcined material after acid washing in sequence to obtain a hard carbon precursor;
mixing the hard carbon precursor and the phosphorus-containing dopant to obtain a mixture;
calcining the mixture for 2-4 hours at 200-500 ℃ in an inert gas environment to obtain a second calcined material;
dissolving the polymer in water and obtaining a polymer solution;
dissolving the second calcined material into the polymer solution, and stirring to obtain a mixed solution;
drying the mixed solution to obtain a mixed material;
and scattering, screening and demagnetizing the mixture to obtain the hard carbon negative electrode material.
In the embodiment of the application, the coarse crushed particles of the hard carbon raw material are in millimeter grade, and the specific size is controlled to be 1mm-5mm, and more preferably 1mm-3mm.
In the embodiment of the present application, the inert gas includes one of nitrogen, helium, neon, and argon.
In the embodiment of the application, the calcining equipment is one or more of a box furnace, a tube furnace, a rotary kiln, a roller kiln, a pushed slab kiln and a shuttle kiln.
In the embodiment of the application, the first reversible capacity of the hard carbon negative electrode material is more than 500mAh/g; the average particle diameter D50 of the hard carbon negative electrode material is 3-12 μm, and preferably 5-10 μm; the specific surface area of the hard carbon negative electrode material is 1m2/g-10m2/g, and more preferably 2m2/g-5m2/g; the hard carbon negative electrode material has a true density of 1.3g/cm3 to 1.8g/cm3, and more preferably 1.40g/cm3 to 1.65g/cm3.
Example 1
In the embodiment of the present application, a method for preparing a hard carbon negative electrode material for a lithium ion secondary battery provided by the present application specifically includes the following steps:
(1) 10kg of coconut shell (hard carbon raw material) is taken to be coarsely crushed, the average size of the coarsely crushed particles is about 2mm, then the crushed particles are placed in a box type furnace, nitrogen is introduced for protection until the oxygen content in the box type furnace is lower than 100ppm, the temperature is raised to 450 ℃, the particles are calcined for 2 hours, 3.5kg of calcined material is obtained, the calcined material is placed in dilute hydrochloric acid with the mass fraction of 10 percent for soaking, the centrifugal separation is carried out after the slow stirring for 2 hours, the obtained powder is dried and then crushed, and the crushed particle size D50 is 7.2 mu m. And sieving to remove large particles, wherein the mesh number of the sieve is 325 meshes, and obtaining the hard carbon precursor.
(2) VC mixing is carried out on the hard carbon precursor obtained in the step (1) and ammonium dihydrogen phosphate according to the mass ratio of 100. And calcining the mixed material in nitrogen gas at 500 ℃ for 2h.
(3) And (3) scattering and screening the fired material obtained in the step (2) to obtain a material with the particle size D50 of 7.4 microns. And adding the sieved material into the polypyrrole solution, stirring at the rotation speed of 300rpm for 4h, drying to cover polypyrrole on the surface of the hard carbon anode material, scattering, sieving and demagnetizing to obtain the hard carbon anode material, wherein the particle size D50 of the hard carbon anode material is 7.5 mu m, the specific surface area of the hard carbon anode material is 2.7m2/g, and the true density of the hard carbon anode material is 1.58g/cm3.
Example 2
The difference from the example 1 is that the hard carbon raw material is phenolic resin, the particle size after coarse crushing is 3mm, the pre-carbonization temperature is 500 ℃, the pre-carbonization time is 4h, the pre-carbonization atmosphere is nitrogen atmosphere, the mass fraction of dilute hydrochloric acid used in the acid cleaning process is less than 12%, and the particle size D50 of the obtained hard carbon precursor is 9.1 μm after centrifugal separation, drying and crushing.
The phosphorus-containing dopant is ammonium phosphate, the mass ratio of the hard carbon precursor to the ammonium phosphate is 100.
And scattering and screening the fired material to obtain a material with the granularity D50 of 9.5 mu m, and compounding polyaniline to cover the surface of the hard carbon negative electrode material to obtain the hard carbon negative electrode material with the granularity D50 of 9.9 mu m, the specific surface area of 2.1m2/g and the true density of 1.63g/cm & lt 3 & gt.
Example 3
The difference from the example 1 is that the hard carbon raw material is petroleum coke, the particle size after coarse crushing is 1mm, the pre-carbonization temperature is 300 ℃, the pre-carbonization time is 7h, the pre-carbonization atmosphere is nitrogen atmosphere, the mass fraction of dilute hydrochloric acid used in the acid cleaning process is less than 8%, and the particle size D50 of the hard carbon precursor obtained after centrifugal separation, drying and crushing is 6.4 μm.
The phosphorus-containing dopant is sodium dihydrogen phosphate, the mass ratio of the hard carbon precursor to the sodium dihydrogen phosphate is 100, the mixing mode is liquid phase mixing, drying is carried out, and the dried material is calcined in nitrogen gas at the temperature of 300 ℃ for 3 hours.
And scattering and screening the fired material to obtain a material with the particle size D50 of 6.5 mu m, and compounding polythiophene to cover the surface of the hard carbon negative electrode material to obtain the hard carbon negative electrode material with the particle size D50 of 6.9 mu m, the specific surface area of 3.8m2/g and the true density of 1.51g/cm < 3 >.
Example 4
The difference from the example 1 is that the hard carbon raw material is starch, the pre-carbonization temperature is 200 ℃, the pre-carbonization time is 9h, the pre-carbonization atmosphere is nitrogen atmosphere, the mass fraction of dilute hydrochloric acid used in the acid cleaning process is less than 6%, and the particle size D50 of the obtained hard carbon precursor is 5.1 μm after centrifugal separation, drying and crushing.
The phosphorus-containing dopant is phosphoric acid, the mass ratio of the hard carbon precursor to the phosphoric acid is 100, the selected mixing mode is solid phase mixing, the mixed material is calcined in nitrogen gas, the calcining temperature is 200 ℃, and the calcining time is 4 hours.
And scattering and screening the fired material to obtain a material with the granularity D50 of 5.2 mu m, and compounding polyimide to cover the surface of the hard carbon anode material to obtain the hard carbon anode material with the granularity D50 of 5.4 mu m, the specific surface area of 4.6m & lt 2 & gt/g and the true density of 1.43g/cm & lt 3 & gt.
Comparative example 1
The difference from example 1 is that in step (1), the raw material is not coarsely crushed, and the rest is the same as example 1, and is not described herein again.
Comparative example 2
The difference from example 1 is that in step (1), after the raw material is coarsely crushed, the particle size is not controlled, and the rest is the same as example 1, and the description is omitted here.
Comparative example 3
The difference from example 1 is that in step (1), the pickling process is not performed, and the rest is the same as example 1, and is not described herein again.
Comparative example 4
The difference from example 1 is that step (2) is not performed, i.e., no phosphorus-containing dopant is added, and the description is omitted as in example 1.
Comparative example 5
The difference from example 1 is that in step (2), the mass ratio of the hard carbon precursor to ammonium phosphate is 100.
Comparative example 6
The difference from example 1 is that in step (2), the mass ratio of the hard carbon precursor to ammonium phosphate is 100.1, and the rest is the same as example 1, and the description is omitted here.
Comparative example 7
The difference from example 1 is that step (3) is not performed, i.e., polymer coating is not used, and the rest is the same as example 1 and will not be described herein.
The carbon negative electrode materials in examples 1 to 5 and comparative examples 1 to 5 were tested by the following methods:
the material particle size range was tested using a malvern laser particle sizer Mastersizer 3000.
The morphology of the material was analyzed using a JSM-7160 scanning electron microscope from Japan Electron corporation.
The material composition elements were analyzed using an X-ray energy spectrometer (X-Max 50) from oxford instruments, uk.
The material was subjected to phase analysis using an XRD diffractometer (X' Pert3 Powder).
The material was tested for specific surface area using a conta NOVA 4000e usa.
The powder true density was measured and calculated using an american macbeck true densitometer (AccuPyc II 1240D).
The carbon negative electrode material obtained in the examples 1 to 5 and the comparative examples 1 to 5 is mixed in pure water according to a mass ratio of a carbon material, conductive carbon black and a binder of 92. The button cells were assembled in an argon-filled glove box, the counter electrode was a metallic lithium sheet, the separator used was Celgard2400 and the electrolyte was 1mol/L of EC/DMC of LiPF6 (Vol 1. And (3) performing charge and discharge tests on the button cell, wherein the voltage interval is 0.005V-1.5V, and the current density is 80mA/g. The first reversible capacity and efficiency of the carbon anode materials in examples and comparative examples were measured.
The carbon negative electrode material in example 1 was evaluated using a pouch full cell, wherein the positive electrode was a mature ternary positive electrode sheet, 1mol/L LiPF6/EC + DMC + EMC (v/v = 1) electrolyte, celgard2400 separator. On a LanD battery test system of Wuhanjinnuo electronics Limited company, the electrochemical performance of the prepared soft package battery is tested, and the test conditions are as follows: and (3) charging and discharging at a constant current of 1.0 ℃ at normal temperature, wherein the charging and discharging voltage is limited to 2.75V-4.2V.
The testing equipment of the button cell and the soft package battery is a LAND battery testing system of Wuhanjinuo electronics company Limited.
Results of performance test of the carbon anode materials of examples 1 to 5 and comparative examples 1 to 5:
table 1 preparation process and components of carbon negative electrode materials in examples 1 to 5 and comparative examples 1 to 5:
table 2 electrochemical performance test data of the carbon anode materials in examples 1 to 5 and comparative examples 1 to 5:
as can be seen from table 1, the hard carbon negative electrode material prepared by the method of the present application has good electrochemical properties, and when it is used as a negative electrode active material of a lithium ion battery, it has excellent cycle performance.
In examples 1 to 5, the electrochemical performance of the hard carbon negative electrode material was greatly influenced by changing the type of the hard carbon raw material, the size of the coarse particles, the particle size of the precursor, the content and dopant of phosphorus, the type of the polymer, and the like. The hard carbon cathode material prepared from different raw materials has different internal structures and pores, and different electrochemical performances. The size of the coarse particles can affect the uniformity of subsequent processes. The particle size of the precursor greatly influences the migration rate of lithium ions, and when the particle size is beyond the upper limit, the cycle performance of the precursor is slightly reduced. Phosphorus doping can increase lithium insertion sites of the hard carbon negative electrode material in the charging and discharging process, so that the specific capacity of the hard carbon negative electrode material is improved. The polymer coating can reduce the side reaction of the carbon negative electrode material and the electrolyte, reduce the irreversible lithium ion loss, contribute to providing the stability of the SEM and improve the cycle performance.
In comparative examples 1 to 2, the raw material was in a large lump without being coarsely crushed, or the particle size of the raw material was not controlled after coarsely crushed, which resulted in non-uniformity of the subsequent carbonization and acid washing purification processes, thereby causing poor material uniformity, and the first reversible capacity and the first efficiency were decreased, and the cycle performance was greatly decreased.
In comparative example 3, the electrochemical performance of the composite cathode material is obviously affected by the inevitable high-content magnetic foreign matters in the hard carbon cathode material without acid cleaning and purification, and the capacity retention rate of the soft package battery with 1C/1C circulation for 2400 weeks is only 78.5%.
In comparative example 4, the reversible capacity of the hard carbon negative electrode material was significantly reduced to only 402.1mAh/g without adding the phosphorus-containing dopant.
In comparative example 5, the mass ratio of the hard carbon precursor to the ammonium phosphate is 100, the reversible capacity of the hard carbon negative electrode material is further improved to 658.8mAh/g, but the cycle performance is obviously reduced, and the capacity retention rate of the soft-package battery after 1C/1C cycle for 2400 weeks is only 69.3%.
In comparative example 6, the mass ratio of the hard carbon precursor to ammonium phosphate was 100.1, and the reversible capacity of the hard carbon anode material was significantly reduced, only 412.7mAh/g.
In comparative example 7, the surface of the material is not coated with the polymer, the cycle performance of the obtained hard carbon negative electrode material is obviously reduced, and the capacity retention rate of the soft-package battery after 1C/1C cycle for 2400 weeks is 76.1%.
The hard carbon negative electrode material for the lithium ion secondary battery and the preparation method thereof have the advantages that:
(1) The hard carbon negative electrode material prepared by the invention contains 0.3-5% of phosphorus element by mass ratio, phosphorus doping can increase lithium insertion sites of the hard carbon negative electrode material in the charging and discharging processes, so that the specific capacity of the hard carbon negative electrode material is improved, the first reversible capacity of the hard carbon negative electrode material is more than 500mAh/g, and the first coulombic efficiency is more than 83%;
(2) In the hard carbon cathode material prepared by the invention, the polymer coating can reduce the side reaction of the carbon cathode material and the electrolyte, reduce the irreversible lithium ion loss, contribute to providing the stability of SEM and simultaneously improve the cycle performance;
(3) The raw materials used by the hard carbon cathode material prepared by the invention are low in price, and the preparation process and equipment are mature, so that the hard carbon cathode material is suitable for large-scale production;
(4) When the hard carbon cathode material prepared by the invention is used as a cathode active material of a lithium ion battery, the cycle performance of the battery can be obviously improved, and the capacity retention rate after 2400 cycles at 1C/1C multiplying power is about 89%.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (1)
1. A method for preparing a hard carbon anode material for a lithium ion secondary battery, the method comprising the steps of:
preparing a hard carbon raw material, a phosphorus-containing dopant and a polymer;
coarsely crushing the hard carbon raw material to obtain coarse crushed materials;
calcining the coarse crushed material for 1 to 10 hours at the temperature of between 200 and 500 ℃ in an inert gas environment to obtain a first calcined material;
carrying out acid washing on the first calcined material by using dilute hydrochloric acid with the mass fraction of less than 15%;
drying, crushing and screening the first calcined material after acid washing in sequence to obtain a hard carbon precursor;
mixing the hard carbon precursor and the phosphorus-containing dopant to obtain a mixture;
calcining the mixture for 2-4 hours at 200-500 ℃ in an inert gas environment to obtain a second calcined material;
dissolving the polymer in water and obtaining a polymer solution;
dissolving the second calcined material into the polymer solution, and stirring to obtain a mixed solution;
drying the mixed solution to obtain a mixed material;
scattering, screening and demagnetizing the mixture to obtain a hard carbon negative electrode material;
the hard carbon anode material includes: the hard carbon negative electrode material comprises a hard carbon precursor, a phosphorus-containing dopant and a polymer, wherein the hard carbon precursor is prepared from a hard carbon raw material, the mass fraction of phosphorus in the phosphorus-containing dopant in the hard carbon negative electrode material is 0.3% -5%, at least one part of the surface of the hard carbon negative electrode material is covered by the polymer, and the mass fraction of the polymer in the hard carbon negative electrode material is 1% -20%; the phosphorus-containing dopant comprises one or more of phosphorus pentoxide, phosphoric acid, sodium dihydrogen phosphate, sodium phosphate, potassium phosphate, ammonium phosphate and ammonium dihydrogen phosphate; the mass ratio of the phosphorus-containing dopant to the hard carbon precursor is (1-20): 100, respectively; the size of the coarse crushed aggregates is 1mm-5mm.
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| CN109301178A (en) * | 2018-08-17 | 2019-02-01 | 福建新峰二维材料科技有限公司 | A kind of sodium Dual-ion cell of the novel carbon negative pole material preparation of doping phosphorus |
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