CN110197897A - Biomass graded porous charcoal/sulphur anode of a kind of nano magnesia doping and its preparation method and application - Google Patents

Biomass graded porous charcoal/sulphur anode of a kind of nano magnesia doping and its preparation method and application Download PDF

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CN110197897A
CN110197897A CN201910427179.1A CN201910427179A CN110197897A CN 110197897 A CN110197897 A CN 110197897A CN 201910427179 A CN201910427179 A CN 201910427179A CN 110197897 A CN110197897 A CN 110197897A
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nano magnesia
porous charcoal
crab shell
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shell base
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黄雅钦
魏坤锐
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Beijing University of Chemical Technology
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    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/02—Electrodes composed of, or comprising, active material
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Abstract

The present invention relates to a kind of nano magnesias to adulterate biomass graded porous charcoal/sulphur anode and its preparation method and application, magnesium ion is anchored using the classifying porous charcoal of the nitrogen oxygen codope crab shell base of high-specific surface area, the fabricated in situ magnesium hydroxide in charcoal hole, calcining obtains the equally distributed nano magnesia doping classifying porous charcoal of crab shell base of nano magnesia, it applies in lithium-sulphur cell positive electrode, the material can be while efficient fixed polysulfide, it ensure that polysulfide is contacted with the good of conductive structure, the balance for realizing polysulfide absorption and recycling, improve the utilization rate of active material, effectively improve the chemical property of lithium-sulfur cell.

Description

A kind of biomass graded porous charcoal of nano magnesia doping/sulphur anode and its preparation side Method and application
Technical field
The invention belongs to lithium-sulfur cell Material Fields, and in particular to a kind of nano magnesia for lithium-sulphur cell positive electrode is mixed Miscellaneous biomass graded porous charcoal/sulphur anode and its preparation method and application.
Background technique
With the rapid development of society, demand of the people to the energy is more and more, but the finiteness of traditional fossil resources The exploration and utilization appealed to clean energy resource are negatively affected caused by environment with it, however since clean energy resource is due to its interval Property and unstability, seem particularly significant to the storage of energy, secondary cell is a kind of effective means of energy storage.
Meanwhile high-energy-density, high circulation stability are appealed in the fast development of portable electronic equipment and electric car The development of battery system, and lithium-sulfur cell is due to its theoretical energy density much higher than lithium ion battery and cheap and easy to get, environment The advantages that friendly and be counted as potential next-generation lithium battery.But it due to the insulating properties of the sulphur of positive active material and is circulated throughout The shuttle effect of more lithium sulfides in journey, the utilization rate of active material is low and capacity attenuation is fast, therefore, construct effective sulphur anode with The stable circulation for guaranteeing the effective use of active material is the critical issue that lithium-sulfur cell looks for that urgently to be resolved.
Summary of the invention
In order to solve the above-mentioned problems in the prior art, the present invention provides a kind of nanometer for lithium-sulphur cell positive electrode Magnesia adulterates biomass graded porous charcoal/sulphur anode and its preparation method and application, to obtain nano magnesia in charcoal hole Successful deposition and the nano magnesia of fine dispersion adulterate the classifying porous Carbon Materials of crab shell base.
The present invention adopts the following technical scheme that a kind of biomass graded porous charcoal of nano magnesia doping/sulphur anode is described Nano magnesia doping ratio be 5%-30%.
In the preferred embodiments of the present invention, the partial size of the nano magnesia is 10-15nm.
In the preferred embodiments of the present invention, the biomass graded porous charcoal is the classifying porous raw material of wood-charcoal of crab shell base Material, specific surface area is in 3000 m2g-1More than, pore volume is 2.1-2.7 cm3g-1, micro pore volume is 0.7-0.9 cm3g-1。
The present invention also protects the nano magnesia to adulterate biomass graded porous charcoal/sulphur anode preparation method, with The nitrogen oxygen classifying porous charcoal of codope crab shell base is matrix, magnesium ion is anchored using nitrogen oxygen codope biomass carbon material, in charcoal hole Middle fabricated in situ magnesium hydroxide, calcining obtains the equally distributed nano magnesia modification porous carbon material of nano magnesia, by this Material carries sulphur and obtains the biomass graded porous charcoal of nano magnesia doping/sulphur anode.Wherein, magnesium hydroxide in-situ deposition In charcoal hole, the nano magnesia and carbon matrix of synthesis have good contact and dispersity, can be used for lithium-sulphur cell positive electrode.
In the preferred embodiments of the present invention, the preparation method the following steps are included:
(1) it using crab shell as raw material, cleans, dry, crush, in tube furnace nitrogen atmosphere, 300- is warming up to 5-10 DEG C/min 330 DEG C, 2-3h is kept the temperature, is carbonized in advance；
(2) the pre- carbonated material of gained in step (1) is mixed with potassium hydroxide, under tube furnace nitrogen atmosphere, with 5-10 DEG C/ Min is warming up to 650-850 DEG C and is carbonized, and keeps the temperature 2-3h, is cooled to room temperature；
(3) resulting materials are repeatedly washed through hydrochloric acid in step (2), and are washed with deionized water to neutrality, by drying, ball milling powder It is broken, obtain the classifying porous Carbon Materials of crab shell base；
(4) the classifying porous charcoal of crab shell base of preparation is mixed in aqueous solution with magnesium acetate, is solution A, ratio depends on setting Doping of the fixed nano magnesia in Carbon Materials carries out magnetic agitation after ultrasonic mixing, guarantees fully dispersed mixing；
It (5) be 1:2 configuration lithium hydroxide solution according to magnesium ion and hydroxide ion molar ratio is solution B, ultrasonic treatment carries out Sufficiently dissolution；
(6) magnetic agitation of solution A is kept, and solution B is added dropwise in A, 8-12h is reacted, reacts fully；
(7) resulting materials in step (6) are repeatedly washed and are dried, be warming up to 500-550 DEG C under nitrogen atmosphere in tube furnace, By the classifying porous charcoal of crab shell base of the magnesium hydroxide adulterated in Carbon Materials calcining nano magnesia doping；
(8) the nano magnesia doping classifying porous Carbon Materials of crab shell base obtained by step (7), which are mixed with sulphur with 1:2-3, to be ground Mill, is warming up to 155 DEG C of holding 10-24h in closed container；
(9) composite material for obtaining step (8) and conductive black, gelatin prepare anode sizing agent, are coated on aluminium foil after ball milling, It is cut into disk after drying, obtains the anode.
In the preferred embodiments of the present invention, in step (2), pre- carbonated material and potassium hydroxide 1:1 in mass ratio It is mixed.
In the preferred embodiments of the present invention, in step (3), the concentration of hydrochloric acid is 1M.
In the preferred embodiments of the present invention, in step (4), magnesium ion concentration is the extremely dilute solution of 4-5mmol/L.
In the preferred embodiments of the present invention, in step (4), the design (calculated) load amount of nano magnesia is 5%-30%.
In the preferred embodiments of the present invention, in step (5), lithium hydroxide concentration is the extremely dilute molten of 8-10nmol/L Liquid.
In the preferred embodiments of the present invention, in step (9), the composite material and conductive black, gelatin Mass ratio is 73-85:8-20:5-15.
In the preferred embodiments of the present invention, in step (9), the diameter of disk is 10-12mm.
The present invention also protects the nano magnesia to adulterate application of the classifying porous charcoal of crab shell base in lithium-sulfur cell.It is logical It crosses active site internal in charcoal skeleton and realizes more balances lithium sulfide absorption and utilized, building active material utilization height, energy The stable lithium-sulphur cell positive electrode of long circulating.
In the preferred embodiments of the present invention, the lithium-sulfur cell adulterates crab shell base with the nano magnesia Classifying porous charcoal is anode, and using metal lithium sheet as cathode, using Celgard2325 type diaphragm, electrolyte is 1M LiTFSI+ 0.4M LiNO3+ DOL/DME(1:1 Vol%), using 2025 formula button cells, lithium sulphur electricity is assembled in argon atmosphere glove box Pond.
Compared with prior art, the present invention has following technical effect that
(1) the classifying porous Carbon Materials of crab shell base that prepare have biggish specific surface area, pore volume, abundant micro- in the present invention Pore structure and native element doping, specific surface area is in 3000m2g-1More than, pore volume 2.1-2.7 cm3g-1, micro pore volume 0.7-0.9 cm3g-1。
(2) the nitrogen oxygen element doping in the classifying porous Carbon Materials of crab shell base is utilized in the present invention, it is nano oxidized synthesizing Stablize magnesium source during magnesium, realizes in-situ deposition, obtain that nano magnesia is well dispersed, the lesser nano magnesia of partial size Adulterate the classifying porous charcoal of crab shell base.The doping partial size about 10-15nm of nano magnesia.
(3) after study, the nano magnesia of special ratios of the present invention adulterates the classifying porous charcoal of crab shell base/sulfur materials application In lithium-sulphur cell positive electrode, porous charcoal framework construction anode structure can be given full play to and internal active sites fix active material Double action, nano magnesia can effectively realize that polysulfide is adsorbed through nano magnesia and in charcoal with well contacting for carbon matrix The balance that recycling is spread on skeleton is conducive to the fixation and effective use of active material, improves the electrochemistry of lithium-sulfur cell Can, capacity is put up to 1053.9mAh g in the head of 0.5C using the modified anode of the material-1, and still have after 300 circulations 632.1mAh g-1Residual capacity.
Detailed description of the invention
It is described further with reference to the accompanying drawing:
Fig. 1 is the high-resolution TEM figure of the gained nano magnesia doping classifying porous Carbon Materials of crab shell base in the embodiment of the present invention 1 Picture；
Fig. 2 be in the embodiment of the present invention 1 and 2 and comparative example 1 and 2 gained positive electrode 0.5C cycle performance figure.
Specific embodiment
It elaborates below to embodiments of the present invention:
Embodiment 1
(1) it using crab shell as raw material, cleans, dry, crush, in tube furnace nitrogen atmosphere, be warming up to 330 DEG C with 5 DEG C/min, protect Warm 2-3h, is carbonized in advance.
(2) the pre- carbonated material of gained in step (1) is mixed with potassium hydroxide 1:1 in mass ratio, in tube furnace nitrogen Under gas atmosphere, 750 DEG C are warming up to 5 DEG C/min and is carbonized, keep the temperature 2-3h, be cooled to room temperature.
(3) resulting materials are repeatedly washed through 1M hydrochloric acid in step (2), and are washed with deionized water to neutrality, by drying, ball It is milled broken, obtains the classifying porous Carbon Materials of crab shell base.
(4) the classifying porous charcoal of crab shell base of preparation is mixed in aqueous solution according to a certain percentage with magnesium acetate, is solution A, ratio depend on doping of the nano magnesia in Carbon Materials of setting, set the doping of nano magnesia as 5%, And magnesium ion concentration is 4-5mmol/L.
It (5) be 1:2 configuration lithium hydroxide solution according to magnesium ion and hydroxide ion molar ratio is solution B, lithium hydroxide Concentration is 8-10mmol/L.
(6) by magnetic agitation that solution A is fully dispersed, it is kept stirring and solution B is added dropwise in A, react 12h, It reacts fully.
(7) material in step (6) is repeatedly washed and is dried, be warming up in tube furnace under nitrogen atmosphere with 3 DEG C/min 500 DEG C, the magnesium hydroxide adulterated in Carbon Materials is calcined to obtain the classifying porous charcoal of crab shell base of nano magnesia doping.
(8) the nano magnesia doping classifying porous Carbon Materials of crab shell base obtained by step (7) are ground mixing with sulphur 1:3 Mill, is warming up to 155 DEG C of holding 12h in closed container.
(9) composite material and conductive black, the gelatin obtained step (8) is prepared anode according to the ratio of 73:20:7 and is starched Expect, be coated on aluminium foil after ball milling, the disk that diameter is 12mm is cut into after drying, prepares anode pole piece, as 5%n-MgO@ CSHPC/S anode.
Embodiment 2
(1) it using crab shell as raw material, cleans, dry, crush, in tube furnace nitrogen atmosphere, be warming up to 330 DEG C with 5 DEG C/min, protect Warm 2-3h, is carbonized in advance.
(2) the pre- carbonated material of gained in step (1) is mixed with potassium hydroxide 1:1 in mass ratio, in tube furnace nitrogen Under gas atmosphere, 750 DEG C are warming up to 5 DEG C/min and is carbonized, keep the temperature 2-3h, be cooled to room temperature.
(3) resulting materials are repeatedly washed through 1M hydrochloric acid in step (2), and are washed with deionized water to neutrality, by drying, ball It is milled broken, obtains the classifying porous Carbon Materials of crab shell base.
(4) the classifying porous charcoal of crab shell base of preparation is mixed in aqueous solution according to a certain percentage with magnesium acetate, is solution A, ratio depend on doping of the nano magnesia in Carbon Materials of setting, set the doping of nano magnesia as 30%, And magnesium ion concentration is 4-5mmol/L.
It (5) be 1:2 configuration lithium hydroxide solution according to magnesium ion and hydroxide ion molar ratio is solution B, lithium hydroxide Concentration is 8-10mmol/L.
(6) by magnetic agitation that solution A is fully dispersed, it is kept stirring and solution B is added dropwise in A, react 12h, It reacts fully.
(7) material in step (6) is repeatedly washed and is dried, be warming up in tube furnace under nitrogen atmosphere with 3 DEG C/min 500 DEG C, the magnesium hydroxide adulterated in Carbon Materials is calcined to obtain the classifying porous charcoal of crab shell base of nano magnesia doping.
(8) the nano magnesia doping classifying porous Carbon Materials of crab shell base obtained by step (7) are ground mixing with sulphur 1:3 Mill, is warming up to 155 DEG C of holding 12h in closed container.
(9) composite material and conductive black, the gelatin obtained step (8) is prepared anode according to the ratio of 73:20:7 and is starched Expect, be coated on aluminium foil after ball milling, the disk that diameter is 12mm is cut into after drying, prepares anode pole piece, as 10%n-MgO@ CSHPC/S anode.
Comparative example 1
(1) it using crab shell as raw material, cleans, dry, crush, in tube furnace nitrogen atmosphere, be warming up to 330 DEG C with 5 DEG C/min, protect Warm 2-3h, is carbonized in advance.
(2) the pre- carbonated material of gained in step (1) is mixed with potassium hydroxide 1:1 in mass ratio, in tube furnace nitrogen Under gas atmosphere, 750 DEG C are warming up to 5 DEG C/min and is carbonized, keep the temperature 2-3h, be cooled to room temperature.
(3) resulting materials in step (2) are repeatedly washed through 1M hydrochloric acid, and are washed with deionized water to neutrality, by drying, Ball mill grinding obtains the classifying porous Carbon Materials of crab shell base.
(4) by the gained classifying porous Carbon Materials of crab shell base in step (3) with sulphur 1:3 mixed grinding, in closed container It is warming up to 155 DEG C of holding 12h.
(5) composite material and conductive black, the gelatin obtained step (4) is prepared anode according to the ratio of 73:20:7 and is starched Expect, be coated on aluminium foil after ball milling, the disk that diameter is 12mm is cut into after drying, is preparing anode pole piece, as CSHPC/S just Pole.
Comparative example 2
Sublimed sulfur and conductive black, gelatin are prepared into anode sizing agent according to the ratio of 63:30:7, are coated on aluminium foil after ball milling, It is cut into the disk that diameter is 12mm after drying, prepares anode pole piece, as common anode.
The synthetic method ensure that nanometer in the nano magnesia doping classifying porous Carbon Materials of crab shell base as seen from Figure 1 The successful load of magnesia, and the partial size of nano magnesia is 10-15nm, is uniformly dispersed in carbon matrix.
As seen from Figure 2, the anode that Examples 1 and 2 are prepared is after the head of 0.5C puts capacity and 300 circulations Residual capacity is all remarkably higher than anode that comparative example 1 and 2, especially embodiment 1 be prepared, and in the head of 0.5C to put capacity reachable 1053.9mAh g-1, and still have 632.1mAh g after 300 circulations-1Residual capacity.
The above content is combine it is specific/further detailed description of the invention for preferred embodiment, cannot recognize Fixed specific implementation of the invention is only limited to these instructions.Without departing from the inventive concept of the premise, these have been described Some replacements or modifications that embodiment is made, all shall be regarded as belonging to protection scope of the present invention.

Claims (10)

1. a kind of nano magnesia adulterates biomass graded porous charcoal/sulphur anode, which is characterized in that the nano magnesia Doping ratio is 5%-30%.
2. nano magnesia according to claim 1 adulterates biomass graded porous charcoal/sulphur anode, which is characterized in that institute The partial size for the nano magnesia stated is 10-15nm, and the biomass graded porous charcoal is the classifying porous Carbon Materials of crab shell base, than Surface area is in 3000 m2g-1More than, pore volume is 2.1-2.7 cm3g-1, micro pore volume is 0.7-0.9 cm3g-1。
3. nano magnesia of any of claims 1 or 2 adulterates biomass graded porous charcoal/sulphur anode preparation method, special Sign is, using the classifying porous charcoal of nitrogen oxygen codope crab shell base as matrix, using nitrogen oxygen codope biomass carbon material anchoring magnesium from Son, the fabricated in situ magnesium hydroxide in charcoal hole, calcining obtain the equally distributed nano magnesia modification porous charcoal of nano magnesia Material load sulphur is obtained the nano magnesia and adulterates biomass graded porous charcoal/sulphur anode by material.
4. preparation method according to claim 3, which comprises the following steps:
(1) it using crab shell as raw material, cleans, dry, crush, in tube furnace nitrogen atmosphere, 300- is warming up to 5-10 DEG C/min 330 DEG C, 2-3h is kept the temperature, is carbonized in advance；
(2) the pre- carbonated material of gained in step (1) is mixed with potassium hydroxide, under tube furnace nitrogen atmosphere, with 5-10 DEG C/ Min is warming up to 650-850 DEG C and is carbonized, and keeps the temperature 2-3h, is cooled to room temperature；
(3) resulting materials are repeatedly washed through hydrochloric acid in step (2), and are washed with deionized water to neutrality, by drying, ball milling powder It is broken, obtain the classifying porous Carbon Materials of crab shell base；
(4) the classifying porous charcoal of crab shell base of preparation is mixed in aqueous solution with magnesium acetate, is solution A, ratio depends on setting Doping of the fixed nano magnesia in Carbon Materials carries out magnetic agitation after ultrasonic mixing, guarantees fully dispersed mixing；
It (5) be 1:2 configuration lithium hydroxide solution according to magnesium ion and hydroxide ion molar ratio is solution B, ultrasonic treatment carries out Sufficiently dissolution；
(6) magnetic agitation of solution A is kept, and solution B is added dropwise in A, 8-12h is reacted, reacts fully；
(7) resulting materials in step (6) are repeatedly washed and are dried, be warming up to 500-550 DEG C under nitrogen atmosphere in tube furnace, The magnesium hydroxide adulterated in Carbon Materials is calcined to obtain the classifying porous charcoal of crab shell base of nano magnesia doping；
(8) the nano magnesia doping classifying porous Carbon Materials of crab shell base obtained by step (7) are with sulphur with 1:(2-3) it mixes and grinds Mill, is warming up to 155 DEG C of holding 10-24h in closed container；
(9) composite material for obtaining step (8) and conductive black, gelatin prepare anode sizing agent, are coated on aluminium foil after ball milling, It is cut into disk after drying, obtains the anode.
5. the preparation method according to claim 4, which is characterized in that in step (2), pre- carbonated material is pressed with potassium hydroxide Mass ratio 1:1 is mixed；In step (3), the concentration of hydrochloric acid is 1M.
6. the preparation method according to claim 4, which is characterized in that in step (4), magnesium ion concentration 4-5mmol/L Extremely dilute solution；The design (calculated) load amount of nano magnesia is 5%-30%.
7. the preparation method according to claim 4, which is characterized in that in step (5), lithium hydroxide concentration is 8- The extremely dilute solution of 10nmol/L.
8. the preparation method according to claim 4, which is characterized in that in step (9), the composite material and conductive charcoal Black, gelatin mass ratio is 73-85:8-20:5-15；The diameter of disk is 10-12mm.
9. nano magnesia of any of claims 1 or 2 adulterates biomass graded porous charcoal/sulphur anode answering in lithium-sulfur cell With.
10. application according to claim 9, which is characterized in that the lithium-sulfur cell is mixed with the nano magnesia The miscellaneous classifying porous charcoal of crab shell base is anode, using metal lithium sheet as cathode, uses Celgard2325 type diaphragm, electrolyte 1M LiTFSI+0.4M LiNO3+ DOL/DME(1:1 Vol%), using 2025 formula button cells, assembled in argon atmosphere glove box Lithium-sulfur cell.
CN201910427179.1A 2019-05-22 2019-05-22 Biomass graded porous charcoal/sulphur anode of a kind of nano magnesia doping and its preparation method and application Pending CN110197897A (en)

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CN111871375A (en) * 2020-08-17 2020-11-03 常州大学 Preparation method and application of biochar with efficient atrazine adsorption performance
CN115078492A (en) * 2022-06-22 2022-09-20 江苏大学 Preparation method and application of BiOX/N-doped biomass charcoal nanocomposite

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Application publication date: 20190903