CN114188537B - Nitrogen-phosphorus-chlorine co-doped carbon material, preparation method thereof and application thereof in lithium battery - Google Patents
Nitrogen-phosphorus-chlorine co-doped carbon material, preparation method thereof and application thereof in lithium battery Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 63
- DEAAQMGATPGXLJ-UHFFFAOYSA-N [N].[P].[Cl] Chemical compound [N].[P].[Cl] DEAAQMGATPGXLJ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000460 chlorine Substances 0.000 claims abstract description 24
- 239000006258 conductive agent Substances 0.000 claims abstract description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000002028 Biomass Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 238000004729 solvothermal method Methods 0.000 claims abstract description 5
- 239000012258 stirred mixture Substances 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 2
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 2
- 229960003750 ethyl chloride Drugs 0.000 claims description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 14
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000010287 polarization Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 235000017060 Arachis glabrata Nutrition 0.000 description 6
- 241001553178 Arachis glabrata Species 0.000 description 6
- 235000010777 Arachis hypogaea Nutrition 0.000 description 6
- 235000018262 Arachis monticola Nutrition 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 235000020232 peanut Nutrition 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000013543 active substance Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 carbon nitrogen chlorine phosphorus Chemical compound 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
Abstract
The co-doped carbon material is prepared from 5-10wt% of nitrogen, 7-30wt% of chlorine and 7-13wt% of phosphorus. The preparation method comprises the following steps: PCl is put into 5 And NH 4 Cl is added into the chlorine-containing organic solvent to carry out solvothermal reaction; adding biomass powder into a solution thermal reaction product, stirring, centrifuging, washing and drying the stirred mixture to obtain a nitrogen-phosphorus-chlorine co-doped carbon material precursor; and under the protection of inert gas, carrying out high-temperature heat treatment on the nitrogen-phosphorus-chlorine co-doped carbon material precursor to obtain the nitrogen-phosphorus-chlorine co-doped carbon material. The nitrogen-phosphorus-chlorine co-doped carbon material is used as a lithium battery conductive agent to be applied to a lithium battery. Compared with the traditional nitrogen-doped carbon material, the nitrogen-phosphorus-chlorine co-doped carbon material can provide more excellent channels for the transmission of ions and electrons, has stronger stability, and improves the energy density and the cycle performance of the lithium ion battery.
Description
Technical Field
The invention belongs to the field of preparation of carbon materials, and particularly relates to a nitrogen-phosphorus-chlorine co-doped carbon material, a preparation method thereof and application thereof in a lithium battery.
Background
In the charge-discharge cycle of the lithium battery, when current passes through the positive and negative pole pieces, a net reaction occurs, which indicates that the electrode loses the original balance state, the electrode potential deviates from the balance potential, and polarization is generated. Lithium battery polarization can be categorized into ohmic polarization, electrochemical polarization, and concentration polarization. The polarization voltage is an important parameter for the electrochemical reaction inside the reaction lithium ion battery, if the polarization voltage is unreasonable for a long time, the precipitation of lithium metal of the negative electrode can be accelerated, and in severe cases, the diaphragm can be pierced to cause short circuit. According to initial experimental data of lithium batteries, the mere dependence on the conductivity of the active material is insufficient to meet the requirement of electron transfer rate, and in order to enable electrons to quickly move and return, the addition of a conductive agent occurs. The primary function of the conductive agent is to increase the electron conductivity. The conductive agent plays a role in collecting micro-current between active substances and between the active substances and the current collector so as to reduce the contact resistance of electrodes, improve the migration rate of electrons in the lithium battery and reduce the polarization of the battery. In addition, the conductive agent can also improve the processability of the pole piece and promote the infiltration of electrolyte to the pole piece, thereby prolonging the service life of the lithium battery.
The traditional lithium ion battery is generally made of carbon materials, but the addition amount of the traditional carbon material conductive agent is up to 0.5% of the mass of the positive electrode material, so that the energy density of the lithium ion battery is affected, and as the energy density requirement of the lithium ion battery is improved, the consumption of the conductive agent is reduced and is better.
The energy density and the cycle performance of the lithium ion battery can be improved by doping the multi-level porous carbon with the different elements, but the doping amount of the different elements in the prior element-doped multi-level porous carbon is lower, the doping elements are single, and the improvement on the energy density and the cycle performance of the lithium ion battery is limited.
Disclosure of Invention
The invention aims to solve the technical problems and overcome the defects and shortcomings in the background art, and provides a nitrogen-phosphorus-chlorine co-doped carbon material, a preparation method thereof and application thereof in a lithium battery conductive agent.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a nitrogen-phosphorus-chlorine co-doped carbon material, wherein in the nitrogen-phosphorus-chlorine co-doped carbon material, the doping amount of nitrogen is 5-10wt%, the doping amount of chlorine is 7-30wt%, and the doping amount of phosphorus is 7-13wt%.
Preferably, the specific surface area of the nitrogen-phosphorus-chlorine co-doped carbon material is 5-2500m 2 Per g, conductivity of 180-4 x 10 3 S/m。
As a general inventive concept, the invention also provides a preparation method of the nitrogen-phosphorus-chlorine co-doped carbon material, which comprises the following steps:
(1) PCl is put into 5 And NH 4 Cl is added into the chlorine-containing organic solvent to carry out solvothermal reaction;
(2) Adding biomass powder into the reaction product obtained in the step (1), stirring, centrifuging, washing and drying the stirred mixture to obtain a nitrogen-phosphorus-chlorine co-doped carbon material precursor;
(3) And under the protection of inert gas, carrying out high-temperature heat treatment on the nitrogen-phosphorus-chlorine co-doped carbon material precursor to obtain the nitrogen-phosphorus-chlorine co-doped carbon material.
In the above preparation method, preferably, in the step (1), the solvothermal reaction temperature is 80-200 ℃ and the reaction time is 1-5h.
In the preparation method, preferably, in the step (2), stirring is performed at normal temperature, and the stirring time is 3-15 hours; the drying is vacuum drying, the drying temperature is 60-120 ℃ and the drying time is 4-24h.
In the above preparation method, preferably, in the step (3), the temperature of the high-temperature heat treatment is 600-1300 ℃, and the time of the heat treatment is 0.5-4 h. It is further preferred that the temperature of the high temperature heat treatment is 1200-1300 ℃, the temperature of the high temperature heat treatment should not be too low, otherwise the stability of the doped chemical bonds is low, resulting in a low conductivity.
In the above preparation method, preferably, in the step (1), the chlorine-containing organic solvent is one or more of chlorobenzene, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, chloroethane, chloropropane, and chlorobutane.
In the above preparation method, preferably, in the step (1), PCl 5 、NH 4 The mass ratio of Cl to the chlorine-containing organic solvent is 1-3:1:0.5-3;
in the step (2), the mass ratio of the biomass powder to the mixture of the nitrogen, phosphorus and chlorine of the reaction product of the step (1) is 1:0.2-2.
The invention also provides an application of the nitrogen-phosphorus-chlorine co-doped carbon material obtained by the preparation method as a conductive agent of a lithium battery in the lithium battery.
In the application, the addition amount of the nitrogen-phosphorus-chlorine co-doped carbon material is preferably 0.005% -0.015% of the mass of the positive electrode material of the lithium battery.
Compared with the prior art, the invention has the advantages that:
(1) Compared with the traditional nitrogen-doped carbon material, the nitrogen-phosphorus-chlorine co-doped carbon material can provide more excellent channels for the transmission of ions and electrons, has stronger stability, and improves the energy density and the cycle performance of the lithium ion battery.
(2) The nitrogen-phosphorus-chlorine co-doped carbon material is used as a conductive agent, the addition amount is small, the addition amount is only five parts per million of the active substance, and is 0.5% of the dosage of the traditional conductive agent, compared with the traditional conductive agent material, the active substance ratio is fully improved and efficiently utilized, and the energy density and the cycle performance of the lithium ion battery can be greatly improved.
(3) According to the preparation method, biomass materials are used as carbon sources, solvents and salts containing hetero atoms are creatively mixed and pre-reacted, so that hetero atom compounds are mutually and uniformly dispersed to form a certain weak chemical bond, the mixed carbon is mixed and carbonized with biomass carbon, the lattice structure of graphite is changed through doping of various hetero atoms, a large number of pores are formed through misplacement doping of elements, and the co-doped carbon materials with high conductivity and high specific surface area can be prepared without adding etching agents such as acid and alkali, the doping amount of the hetero atoms can reach more than 20%, and the preparation method is simple, low in cost and beneficial to realization of scale and industrialization.
Drawings
FIG. 1 is an electron microscopic view of a nitrogen-phosphorus-chlorine co-doped porous carbon material prepared in example 6.
FIG. 2 is a graph showing the desorption of the nitrogen-phosphorus-chlorine co-doped porous carbon materials prepared in examples 4-7.
Fig. 3 is a graph of the cycling performance of the nitrogen-phosphorus-chlorine co-doped porous carbon materials prepared in examples 6 and 7 and lithium ion batteries prepared with commercial conductive agents.
Fig. 4 is a graph of the capacity of lithium ion batteries made with the nitrogen-phosphorus-chlorine co-doped porous carbon materials prepared in examples 6 and 7 and commercial conductive agents.
Detailed Description
The invention will be described more fully hereinafter with reference to the accompanying drawings and preferred embodiments in order to facilitate an understanding of the invention, but the scope of the invention is not limited to the following specific embodiments.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
the preparation method of the nitrogen-phosphorus-chlorine co-doped carbon material comprises the following steps:
(1) Accurately weighing 100g of peanut shells, cleaning, airing, crushing and sieving with a 40-mesh sieve to obtain peanut shell powder for later use;
(2) 50g of PCl are weighed separately 5 And 50g of NH 4 Cl is slowly added into a hydrothermal reaction kettle filled with 100g of dichloromethane, and stirred and reacted for 4 hours at 120 ℃ to obtain a mixture containing nitrogen, phosphorus and chlorine;
(3) Adding the peanut shell powder prepared in the step (1) into the mixture containing nitrogen, phosphorus and chlorine obtained in the step (2), stirring for 7 hours at normal temperature, collecting the stirred mixture into a centrifuge tube, centrifuging at the rotating speed of 4000r/min for 10 minutes, sucking away upper liquid, adding ionized water into the centrifuge tube, repeating for 5 times, discarding supernatant liquid, collecting solid products in the centrifuge tube, and vacuum-drying at 80 ℃ for 8 hours to obtain a nitrogen, phosphorus and chlorine co-doped carbon material precursor;
(4) And under the protection of nitrogen, carrying out heat treatment on the nitrogen-phosphorus-chlorine co-doped carbon material precursor for 3 hours at 700 ℃ in a tube furnace, and collecting a final product to obtain the nitrogen-phosphorus-chlorine co-doped porous carbon material, which is named as NPCL-700.
Example 2:
the preparation method of the nitrogen-phosphorus-chlorine co-doped carbon material of this embodiment is different from that of embodiment 1 only in the temperature of the heat treatment in step (4), the temperature of the heat treatment in this embodiment is 800 ℃, and the prepared nitrogen-phosphorus-chlorine co-doped carbon material is referred to as NPCL-800.
Example 3:
the preparation method of the nitrogen-phosphorus-chlorine co-doped carbon material in this embodiment is different from that in embodiment 1 only in that the temperature and time of the heat treatment in step (4) are different, the temperature of the heat treatment in this embodiment is 900 ℃, the time of the heat treatment is 2 hours, and the prepared nitrogen-phosphorus-chlorine co-doped carbon material is referred to as NPCL-900.
Example 4:
the preparation method of the nitrogen-phosphorus-chlorine co-doped carbon material in this embodiment is different from that in embodiment 1 only in that the temperature and time of the heat treatment in step (4) are different, the temperature of the heat treatment in this embodiment is 1000 ℃, the time of the heat treatment is 2 hours, and the prepared nitrogen-phosphorus-chlorine co-doped carbon material is NPCL-1000.
Example 5:
the preparation method of the nitrogen-phosphorus-chlorine co-doped carbon material in this embodiment is different from that in embodiment 1 only in that the temperature and time of the heat treatment in step (4) are different, the temperature of the heat treatment in this embodiment is 1100 ℃, the time of the heat treatment is 2 hours, and the prepared nitrogen-phosphorus-chlorine co-doped carbon material is referred to as NPCL-1100.
Example 6:
the difference between the preparation method of the nitrogen-phosphorus-chlorine co-doped carbon material in this embodiment and embodiment 1 is that the temperature and time of the heat treatment in step (4) are different, the temperature of the heat treatment in this embodiment is 1200 ℃, the time of the heat treatment is 1h, the prepared nitrogen-phosphorus-chlorine co-doped carbon material is NPCL-1200, an electron microscope image is shown in fig. 1, it can be seen that the particle size of the material is relatively uniform, and the morphology is mostly spherical particles.
Example 7:
the preparation method of the nitrogen-phosphorus-chlorine co-doped carbon material in this embodiment is different from that in embodiment 1 only in that the temperature and time of the heat treatment in step (4) are different, the temperature of the heat treatment in this embodiment is 1300 ℃, the time of the heat treatment is 0.5h, and the prepared nitrogen-phosphorus-chlorine co-doped carbon material is NPCL-1300.
Example 8:
the preparation method of the nitrogen-phosphorus-chlorine co-doped carbon material in this embodiment is different from that in embodiment 3 only in that the protective atmosphere in the heat treatment process in step (4) is different, and argon is introduced in this embodiment.
Example 9:
the preparation method of the nitrogen-phosphorus-chlorine co-doped carbon material in this embodiment is different from that in embodiment 4 only in that the protective atmosphere in the heat treatment process in step (4) is different, and argon is introduced in this embodiment.
Example 10:
the preparation method of the nitrogen-phosphorus-chlorine co-doped carbon material in this embodiment is different from that in embodiment 5 only in that the protective atmosphere in the heat treatment process in step (4) is different, and argon is introduced in this embodiment.
Comparative example:
the preparation method of the carbon material of the comparative example comprises the following steps:
(1) Accurately weighing 100g of peanut shells, cleaning, airing, crushing and sieving with a 40-mesh sieve to obtain peanut shell powder for later use;
(2) 50g of PCl are weighed separately 5 And 50g of NH 4 Cl is slowly added into a hydrothermal reaction kettle filled with 100g of dichloromethane, and stirred for 2 hours at 120 ℃ to obtain a mixture containing nitrogen, phosphorus and chlorine;
(3) Adding the peanut shell powder prepared in the step (1) into the mixture containing nitrogen, phosphorus and chlorine obtained in the step (2), and stirring for 7 hours at normal temperature to obtain a mixture;
(4) And under the protection of nitrogen, carrying out heat treatment on the obtained mixture in a tube furnace at 1200 ℃ for 1h, and collecting a final product to obtain the nitrogen-phosphorus-chlorine co-doped porous carbon material.
The results of the carbon nitrogen chlorine phosphorus element ratio tests (elemental analyzer EDX 4500P), specific surface area test (JB-1), conductivity test (FT-301) prepared in examples 1-10 and comparative example are shown in Table 1 below.
Table 1 carbon, nitrogen, chlorine, phosphorus element ratio and performance data prepared in examples and comparative examples
Fig. 2 is an adsorption-desorption graph of the nitrogen-phosphorus-chlorine co-doped porous carbon materials prepared in examples 4-7 according to the present invention, and it can be seen from the graph that examples 4-7 all have a certain adsorption-desorption hysteresis, which indicates that the porous carbon material not only has a large number of micropores, but also has a certain amount of mesopores.
The nitrogen-phosphorus-chlorine co-doped porous carbon materials prepared in examples 6 to 7 were added as a conductive agent to a lithium battery cathode material in an amount of 0.005% by mass of the cathode material, and as a comparison, a commercial conductive agent (termi SP) was added as a conductive agent to a lithium battery cathode material in an amount of 0.5% by mass of the cathode material. Through homogenate, coating, rolling, slitting and tabletting, the cylindrical battery 18650 is assembled by matching with a graphite negative electrode plate with the same specification. After each positive electrode material is prepared into a lithium ion battery, the charge and discharge performance test is carried out in a Xinwei battery tester CT-9000, the charge and discharge multiplying power is 1C-15C, and the cycle test is completed at room temperature of 25 ℃. After the test is completed, the cycle performance chart is shown in fig. 3. As can be seen from fig. 3, under the conditions of different multiplying power and circulation times, the nitrogen-phosphorus-chlorine co-doped porous carbon material of the invention has excellent circulation performance after being used as a conductive agent material of a lithium ion secondary battery under the condition of adding only 0.005%, and the circulation performance of the lithium ion batteries prepared in the example 6 and the example 7 is obviously better than that of a commercial conductive agent (high SP). As can be seen from fig. 4, the 18650 cylindrical batteries of example 6 and example 7 had test capacities of 2753mAh and 2735mAh, respectively, which are higher than 2610mAh of the commercial conductive agent, significantly improving the energy density of the batteries.
Claims (6)
1. The preparation method of the nitrogen-phosphorus-chlorine co-doped carbon material is characterized in that in the nitrogen-phosphorus-chlorine co-doped carbon material, the doping amount of nitrogen is 5-10wt%, the doping amount of chlorine is 7-30wt%, and the doping amount of phosphorus is 7-13wt%, and the preparation method comprises the following steps:
(1) PCl is put into 5 And NH 4 Cl is added into the chlorine-containing organic solvent to carry out solvothermal reaction; the temperature of the solvothermal reaction is 80-200 ℃, and the reaction time is 1-5h;
(2) Adding biomass powder into the reaction product obtained in the step (1), stirring, centrifuging, washing and drying the stirred mixture to obtain a nitrogen-phosphorus-chlorine co-doped carbon material precursor;
(3) And under the protection of inert gas, carrying out high-temperature heat treatment on the nitrogen-phosphorus-chlorine co-doped carbon material precursor to obtain the nitrogen-phosphorus-chlorine co-doped carbon material, wherein the temperature of the high-temperature heat treatment is 1000-1300 ℃, and the heat treatment time is 0.5-4 h.
2. The preparation method according to claim 1, wherein in the step (2), stirring is performed at normal temperature for 3 to 15 hours; the drying is vacuum drying, the drying temperature is 60-120 ℃ and the drying time is 4-24h.
3. The process according to any one of claims 1 to 2, wherein in step (1), the chlorine-containing organic solvent is one or more of chlorobenzene, dichloromethane, chloroform, tetrachloromethane, dichloroethane, chloroethane, chloropropane, and chlorobutane.
4. The process according to any one of claims 1 to 2, wherein in step (1), PCl 5 、NH 4 The mass ratio of Cl to the chlorine-containing organic solvent is 1-3:1:0.5-3;
in the step (2), the mass ratio of the biomass powder to the reaction product of the step (1) is 1:0.2-2.
5. Use of the nitrogen-phosphorus-chlorine co-doped carbon material obtained by the preparation method of any one of claims 1 to 4 as a lithium battery conductive agent in a lithium battery.
6. The use according to claim 5, wherein the addition amount of the nitrogen-phosphorus-chlorine co-doped carbon material is 0.005% -0.015% of the mass of the positive electrode material of the lithium battery.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111368825.5A CN114188537B (en) | 2021-11-18 | 2021-11-18 | Nitrogen-phosphorus-chlorine co-doped carbon material, preparation method thereof and application thereof in lithium battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111368825.5A CN114188537B (en) | 2021-11-18 | 2021-11-18 | Nitrogen-phosphorus-chlorine co-doped carbon material, preparation method thereof and application thereof in lithium battery |
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| CN114188537A CN114188537A (en) | 2022-03-15 |
| CN114188537B true CN114188537B (en) | 2024-03-22 |
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