CN117069097A - Preparation method and application of hierarchical pore hard carbon material - Google Patents
Preparation method and application of hierarchical pore hard carbon material Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 9
- 239000003575 carbonaceous material Substances 0.000 title claims description 13
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 26
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 241000609240 Ambelania acida Species 0.000 claims abstract description 15
- 239000010905 bagasse Substances 0.000 claims abstract description 15
- 229920002678 cellulose Polymers 0.000 claims abstract description 9
- 239000001913 cellulose Substances 0.000 claims abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 11
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000007833 carbon precursor Substances 0.000 abstract description 4
- 239000002082 metal nanoparticle Substances 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 description 15
- 238000009826 distribution Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 229910021384 soft carbon Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical group [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004676 glycans Polymers 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 150000004804 polysaccharides Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method and application of hierarchical pore hard carbon, which uses bagasse rich in cellulose as a hard carbon precursor, and metal nano particles as a pore-forming agent to construct a multilevel Kong Yingtan material, so that the problems of low initial coulomb efficiency, poor circulation stability and low sodium storage performance of a sodium ion battery are solved.
Description
Technical field:
the invention relates to the technical field of sodium ion battery anode materials, in particular to a preparation method and application of hierarchical pore hard carbon.
The background technology is as follows:
the research of the novel energy storage system which is safe and reliable at present becomes particularly important. In the novel electrochemical energy storage system, the lithium ion battery has been widely applied to the fields of smart power grids, electric vehicles, mobile communication and the like due to the advantages of high capacity, long cycle life and the like, however, the problems of low storage amount, uneven distribution, high price and the like of lithium resources in the crust are increasingly prominent in recent years. The development of a novel electrochemical energy storage system with low price and rich resource reserves is particularly important.
Compared with the problems of lithium resources, the sodium resources are abundant in reserves, wide in distribution and low in price, and the physical and chemical properties of the sodium resources are close to those of the lithium in the same main group in the periodic table of chemical elements, so that the sodium ion battery shows wide development space and application scene in an energy storage system. However, compared with a lithium ion battery, the radius of sodium ions is larger, so that the sodium ions migrate slowly and expand seriously in volume in the deintercalation process, and therefore, the search for a proper electrode material is a key for promoting the development of the sodium ion battery. For sodium ion batteries, the positive electrode material is mainly composed of layered oxides and polyanion compounds, and the positive electrode material exhibits good energy density and cyclicity. The matched cathode material is still in a short plate at present, and the development of the high-performance cathode material is a hot spot and an important point of the sodium ion battery at present.
The negative electrode material of the sodium ion battery is mainly divided into carbon base, metal alloy, metal oxide, other compounds and the like. Compared with other materials, the carbon-based material is considered as the most promising anode material due to the advantages of abundant resources, low price, simple preparation process and the like. Currently, carbon-based materials mainly include graphite, soft carbon, and hard carbon. However, the carbon material of graphite type increases the difficulty of intercalation and deintercalation of sodium ions between graphite layers due to the larger radius of sodium ions, thereby resulting in reduced performance. Soft carbon refers to an amorphous carbon material with higher order, and can be completely graphitized at a temperature above 2800 ℃; the prior soft carbon material has the advantages of low cost, high first charge and discharge efficiency, but lower gram capacity, and the main flow capacity is generally 220-240mA h g -1 The method comprises the steps of carrying out a first treatment on the surface of the Compared with other carbon materials, the hard carbon has higher gram capacity of 300mA h g -1 However, the problems of low initial coulombic efficiency and poor long-cycle stability seriously hamper the application of hard carbon in sodium ion batteries.
The invention comprises the following steps:
the invention aims to provide a preparation method and application of hierarchical pore hard carbon, which uses bagasse rich in cellulose as a hard carbon precursor, uses metal nano particles as a pore-forming agent, constructs a multilevel Kong Yingtan material, and applies the material to a sodium ion battery so as to solve the problems of low initial coulomb efficiency, poor circulation stability and low sodium storage performance of the sodium ion battery.
The invention is realized by the following technical scheme:
a method for preparing hierarchical pore hard carbon, the method comprising the steps of:
1) With ferric nitrate (Fe (NO) 3 ) 3 ) Cobalt nitrate (Co (NO) 3 ) 2 ) Nickel nitrate (Ni (NO) 3 ) 2 ) Taking one of the metal salts as a raw material, taking deionized water as a solvent, and performing ultrasonic treatment and stirring to form a uniform solution A with the metal ion concentration of 0.5-2.0 wt%;
2) Adding bagasse rich in cellulose into the uniform solution A, and rapidly stirring under the protection of inert gas until a uniform solution B is formed; wherein, the bagasse accounts for 90 to 98 percent of the total mass; placing the mixture in a high-pressure reaction kettle, placing the mixture in a temperature programming drying box, carrying out temperature programming, centrifuging, washing and drying the solid obtained by the reaction to obtain solid powder; the temperature programming is firstly carried out to 120-140 ℃ at a temperature rising rate of 5 ℃/min, the constant temperature time is 6-12 h, then the temperature is firstly carried out to 180-200 ℃ at a temperature rising rate of 5 ℃/min, and the constant temperature time is 6-12 h;
3) Placing the solid powder obtained in the step 2) into a tube furnace, heating to 800-1000 ℃ at a heating rate of 5 ℃/min under the protection of inert gas, and naturally cooling to room temperature after keeping the temperature for 2-4 hours to obtain black powder;
4) Impregnating the black powder obtained in the step 3) to a concentration of 0.5 to 2.0mol L -1 Dipping for 4-6 h to remove the metal catalyst, and obtaining the hard carbon material with a multi-stage pore structure.
The inert gas is one of nitrogen and argon.
The acid liquor in the step 4) is one of sulfuric acid, hydrochloric acid and nitric acid.
The raw material takes bagasse rich in cellulose as a hard carbon precursor, which is biomass and waste, so that the raw material is low in cost and easy to obtain. The addition of the metal particles not only contributes to the construction of the multistage holes, but also promotes the carbonization of bagasse. The obtained multilevel Kong Yingtan material has a multilevel pore structure of micropores, mesopores, macropores and the like. The porous structure has the characteristics of rich pore structure, adjustable pore diameter distribution and the like, and the comprehensive performance of the sodium ion battery is greatly improved.
The invention also protects the multistage Kong Yingtan obtained by the preparation method and application thereof, and is mainly used as a negative electrode material of a sodium ion battery.
The invention also protects a sodium ion battery, wherein the multistage Kong Yingtan obtained by the preparation method is taken as a negative electrode, and a sodium sheet is taken as a positive electrode.
The beneficial effects of the invention are as follows:
1) According to the invention, bagasse rich in cellulose is used as a hard carbon precursor, the unique macromolecular polysaccharide structure of cellulose is beneficial to the improvement of hard carbon yield and the regulation and control of aperture size, metal nano particles are pore formers, multistage Kong Yingtan materials are constructed, the sizes of the metal nano particles are effectively regulated and controlled by utilizing a temperature programming pretreatment mode, so that the generation of multistage pore hard carbon materials is promoted, the problems of low initial coulomb efficiency, poor circulation stability, low sodium storage performance and the like of a sodium ion battery are effectively solved, and the commercial process of the sodium ion battery is promoted.
2) The addition of the metal particles not only contributes to the construction of the multistage holes, but also promotes the carbonization of bagasse.
3) The multistage Kong Yingtan material obtained by the invention has multistage pore structures such as micropores, mesopores, macropores and the like. The comprehensive performance of the sodium ion battery is greatly improved due to the characteristics of rich pore structure, adjustable pore diameter distribution and the like.
Description of the drawings:
FIG. 1 is a graph showing pore size distribution of hard carbon generated in a system without addition of metal salt obtained in comparative example 1;
FIG. 2 shows the composition of the iron nitrate (Fe (NO) 3 ) 3 ) A hard carbon pore size distribution diagram with salt as a pore-forming agent;
FIG. 3 shows a method of treating a metal oxide with ferric nitrate (Fe (NO) 3 ) 3 ) And a sodium ion battery performance diagram constructed by hard carbon with salt as a pore-forming agent.
The specific embodiment is as follows:
the following is a further illustration of the invention and is not a limitation of the invention.
Example 1: preparation of hierarchical pore hard carbon material
The method is completed according to the following steps:
(1) With ferric nitrate (Fe (NO) 3 ) 3 ) Is metal salt, deionized water is solvent, ultrasonic treatment and stirring are carried out until a uniform solution A is formed, wherein Fe 3+ The concentration of (2) was 0.5wt%.
(2) Adding a certain amount of bagasse rich in cellulose into the uniformly dispersed solution A, and rapidly stirring under the protection of inert gas nitrogen at a stirring speed of 400rpm until a uniform solution B is formed, wherein the bagasse accounts for 90wt% of the total mass; and (3) placing the solution B in a high-pressure reaction kettle, placing in a temperature programming drying oven, firstly heating to 120 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 6 hours, then heating to 180 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 6 hours, centrifuging, washing and drying the obtained solid to obtain solid powder, wherein the washing liquid is deionized water.
(3) And (3) placing the solid powder obtained in the step (2) into a tube furnace, heating to 1000 ℃ at a heating rate of 5 ℃/min under the protection of inert gas nitrogen, keeping the temperature for 2 hours, and naturally cooling to room temperature to obtain black powder.
(4) Impregnating the black powder obtained in the step (3) to 0.5mol L -1 Immersing for 6 hours at room temperature to remove the metal catalyst, and finally obtaining the hard carbon material with the multi-stage pore structure. The pore size distribution is shown in FIG. 2.
As can be seen from fig. 2, the iron nitrate (Fe (NO 3 ) 3 ) In a system with salt as a pore-forming agent, the hard carbon has abundant micropores, mesopores and macropores, and has larger pore size, so that the developed pore-size channel is beneficial to the rapid transfer of sodium ions in the electrolyte and the rapid deintercalation of the sodium ions. A sodium ion battery was constructed using the hard carbon obtained in example 1 as the negative electrode and a sodium sheet as the positive electrode, and the specific capacity thereof was as shown in FIG. 3, and it can be seen from the figure that the voltage window of the battery was 0 to 3.0V, and the specific capacity was 305mA h g -1 Has higher specific capacity of battery.
Comparative example 1:
with reference to the example 1 of the present invention,the difference is that in the step (1), NO ferric nitrate (Fe (NO) 3 ) 3 )。
Dispersing the bagasse rich in cellulose in deionized water, and rapidly stirring under the protection of inert gas nitrogen at a stirring speed of 400rpm until a uniform solution B is formed, wherein the bagasse accounts for 90wt% of the total mass; and (3) placing the solution B in a high-pressure reaction kettle, placing in a temperature programming drying oven, firstly heating to 120 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 6 hours, then heating to 180 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 6 hours, centrifuging, washing and drying the obtained solid to obtain solid powder, wherein the washing liquid is deionized water.
(3) And (3) placing the solid powder obtained in the step (2) into a tube furnace, heating to 1000 ℃ at a heating rate of 5 ℃/min under the protection of inert gas nitrogen, keeping the temperature for 2 hours, and naturally cooling to room temperature to obtain black powder.
The pore size distribution diagram of the hard carbon material obtained finally is shown in figure 1.
As can be seen from fig. 1, the hard carbon produced in the system without the added metal salt has micropores, mesopores and macropores, wherein the micropore and mesopore volumes are relatively small.
As can be seen from the comparison of example 1 and comparative example 1, the addition of the metal particles not only contributes to the construction of the multistage holes, but also promotes carbonization of bagasse.
Example 2:
reference example 1 is different in that in step (1), iron nitrate (Fe (NO) 3 ) 3 ) Replaced by cobalt nitrate (Co (NO) 3 ) 2 )。
Example 3:
referring to example 1, the temperature programming procedure of step (2) was first to raise the temperature to 140℃at a temperature raising rate of 5℃per minute for a constant temperature of 6 hours, and then to raise the temperature to 200℃at a temperature raising rate of 5℃per minute for a constant temperature of 6 hours.
Example 4:
reference example 1 is different in that step (3) is: and (3) placing the solid powder obtained in the step (2) into a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under the protection of inert gas nitrogen, keeping the temperature for 2 hours, and naturally cooling to room temperature to obtain black powder.
Claims (6)
1. A method for preparing hierarchical pore hard carbon, which is characterized by comprising the following steps:
1) Taking one of ferric nitrate, cobalt nitrate and nickel nitrate as a raw material, taking deionized water as a solvent, and performing ultrasonic treatment and stirring to form a uniform solution A with the metal ion concentration of 0.5-2.0 wt%;
2) Adding bagasse rich in cellulose into the uniform solution A, and rapidly stirring under the protection of inert gas until a uniform solution B is formed; wherein, the bagasse accounts for 90 to 98 percent of the total mass; placing the mixture in a high-pressure reaction kettle, placing the mixture in a temperature programming drying box, carrying out temperature programming, centrifuging, washing and drying the solid obtained by the reaction to obtain solid powder; the temperature programming is firstly carried out to 120-140 ℃ at a temperature rising rate of 5 ℃/min, the constant temperature time is 6-12 h, then the temperature is firstly carried out to 180-200 ℃ at a temperature rising rate of 5 ℃/min, and the constant temperature time is 6-12 h;
3) Placing the solid powder obtained in the step 2) into a tube furnace, heating to 800-1000 ℃ at a heating rate of 5 ℃/min under the protection of inert gas, and naturally cooling to room temperature after keeping the temperature for 2-4 hours to obtain black powder;
4) Impregnating the black powder obtained in the step 3) to a concentration of 0.5 to 2.0mol L -1 Dipping for 4-6 h to obtain the hard carbon material with a hierarchical pore structure.
2. The method of claim 1, wherein the inert gas is one of nitrogen and argon.
3. The method according to claim 1, wherein the acid in step 4) is one of sulfuric acid, hydrochloric acid and nitric acid.
4. Multistage Kong Yingtan obtained by the process according to claim 1.
5. The use of the hierarchical porous hard carbon obtained by the preparation method according to claim 1, as a negative electrode material for sodium ion batteries.
6. A sodium ion battery having a negative electrode of multistage Kong Yingtan obtained by the method of claim 1 and a positive electrode of sodium sheet.
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