CN114023940A - Application of cobalt-nitrogen doped carbon material in positive electrode of all-solid-state lithium-sulfur battery and preparation - Google Patents
Application of cobalt-nitrogen doped carbon material in positive electrode of all-solid-state lithium-sulfur battery and preparation Download PDFInfo
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 39
- YDVGDXLABZAVCP-UHFFFAOYSA-N azanylidynecobalt Chemical compound [N].[Co] YDVGDXLABZAVCP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002131 composite material Substances 0.000 claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
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- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 3
- 238000005245 sintering Methods 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 61
- 239000003792 electrolyte Substances 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
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- 239000007774 positive electrode material Substances 0.000 claims description 15
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- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 claims description 14
- 229910011201 Li7P3S11 Inorganic materials 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 239000010406 cathode material Substances 0.000 claims description 11
- 229910052738 indium Inorganic materials 0.000 claims description 11
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- 238000001291 vacuum drying Methods 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
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- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229910000846 In alloy Inorganic materials 0.000 claims description 6
- 238000010306 acid treatment Methods 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 claims description 4
- 229910010848 Li6PS5Cl Inorganic materials 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910006580 β-Li3PS4 Inorganic materials 0.000 claims description 4
- 229910020676 Co—N Inorganic materials 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000006245 Carbon black Super-P Substances 0.000 claims description 2
- 229910010854 Li6PS5Br Inorganic materials 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 239000011593 sulfur Substances 0.000 abstract description 47
- 229910052717 sulfur Inorganic materials 0.000 abstract description 47
- 239000010405 anode material Substances 0.000 abstract description 33
- 239000007784 solid electrolyte Substances 0.000 abstract description 13
- 238000011068 loading method Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000005077 polysulfide Substances 0.000 abstract description 5
- 229920001021 polysulfide Polymers 0.000 abstract description 5
- 150000008117 polysulfides Polymers 0.000 abstract description 5
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 238000002485 combustion reaction Methods 0.000 abstract description 2
- 239000011258 core-shell material Substances 0.000 abstract description 2
- 239000011244 liquid electrolyte Substances 0.000 abstract description 2
- 230000002441 reversible effect Effects 0.000 abstract description 2
- 239000004020 conductor Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000003273 ketjen black Substances 0.000 description 23
- 239000011149 active material Substances 0.000 description 12
- 239000012300 argon atmosphere Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- 239000011324 bead Substances 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- XAQHXGSHRMHVMU-UHFFFAOYSA-N [S].[S] Chemical compound [S].[S] XAQHXGSHRMHVMU-UHFFFAOYSA-N 0.000 description 4
- 229940011182 cobalt acetate Drugs 0.000 description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 230000007480 spreading Effects 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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Abstract
An application and a preparation of a cobalt-nitrogen doped carbon material in a positive electrode of an all-solid-state lithium-sulfur battery relate to the lithium-sulfur battery. The cobalt-nitrogen doped carbon material is prepared by dispersing a carbon source, a nitrogen source and a cobalt source serving as raw materials in an organic solvent, ultrasonically stirring and dispersing, and sintering at a high temperature. The conductive material can be used as a conductive matrix material to be applied to the preparation of the all-solid-state lithium-sulfur battery composite anode material, so as to prepare the all-solid-state lithium-sulfur battery. The cobalt-nitrogen doped carbon material has a good core-shell structure, relieves the volume expansion effect of sulfur, improves the reversible specific capacity and cycle life of the battery, and the battery can be 50 wt% and 6mg/cm2High sulfur ofAt a content and high sulfur surface loading of 0.2mA/cm2The current density is circulated, the specific discharge capacity of the first circle is more than 1200mAh/g, and the capacity retention rate is more than or equal to 90 percent after 30 cycles; because the solid electrolyte is adopted to replace the organic liquid electrolyte, the shuttle effect of polysulfide is not involved, and the safety problems of combustion, leakage and the like can be solved.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur batteries, in particular to application and preparation of a cobalt-nitrogen doped carbon material in an all-solid-state lithium-sulfur battery positive electrode.
Background
With the rapid development of portable electronic devices and electric vehicles, the conventional lithium ion battery is not enough to meet the current requirements of people, and the development of a new generation of secondary battery is imminent. Lithium-sulfur batteries have been the focus of recent research by virtue of their high energy density and high theoretical specific capacity, and they also have the advantages of low cost and environmental friendliness. However, in conventional liquid lithium-sulfur batteries, the formation of soluble lithium polysulfide intermediates and their dissolution and diffusion in the electrolyte can lead to loss of positive active material and corrosion of metallic lithium, reducing the coulombic efficiency of the battery. Moreover, the use of organic electrolytes presents the risks of leakage and flammability.
In all solid-state lithium sulfur batteries, the sulfur conversion can fundamentally address the polysulfide shuttling effect since it does not involve the formation of soluble polysulfides. On the other hand, the inherent rigidity and non-flammability of solid electrolytes can reduce the risk of ignition, significantly improving battery safety. However, the practical application of the all-solid-state lithium-sulfur battery is still a great challenge, firstly, sulfur is an electronic and ionic insulator, the electrochemical reaction of sulfur strongly depends on the electronic and ionic transmission through the three-phase interface among sulfur, solid electrolyte and conductive additive, and in order to improve the utilization rate of sulfur, more conductive agent and solid electrolyte are usually added to transmit electrons/ions, so as to reduce the content of active substances in the composite positive electrode and further reduce the energy density of the battery; and secondly, the density difference between sulfur and lithium sulfide causes large volume change in the charging and discharging process, so that electrochemical contact deterioration is easily caused, and the rapid decline of the capacity is caused. Therefore, research and development of a sulfur cathode material having a high sulfur active material content and being cycle-stable is crucial to promote practical development of an all-solid lithium-sulfur battery.
Disclosure of Invention
The first purpose of the invention is to provide a cobalt-nitrogen doped carbon material with high sulfur active substance content and good cycle stability.
The second objective of the invention is to provide a preparation method of the cobalt nitrogen doped carbon material.
The third purpose of the invention is to provide an application of the cobalt nitrogen doped carbon material in the cathode material of the all-solid-state lithium-sulfur battery.
A Co-N doped carbon material is prepared from carbon source, nitrogen source and Co source through dispersing in organic solvent, ultrasonic stirring, and high-temp sintering3O4/Co-N-C。
The preparation method of the cobalt-nitrogen doped carbon material comprises the following steps:
1) acid treatment of the carbon source; carrying out oil bath reflux treatment on the carbon source by using concentrated acid, cooling to room temperature, removing residual acid, and carrying out vacuum drying;
2) preparing materials; adding a nitrogen source, a cobalt source and the acid-treated carbon source in the step 1) into an organic solvent;
3) ultrasonic dispersion; step 2), the ingredients form a homogeneous suspension under the action of ultrasonic dispersion;
4) drying; heating and stirring the homogeneous suspension obtained in the step 3) until the solvent is completely evaporated to dryness to obtain precursor powder;
5) pyrolyzing; pyrolyzing the precursor powder obtained in the step 4) at high temperature in an inert atmosphere to obtain a black powder sample, namely the cobalt-nitrogen doped carbon material.
In the step 1), the concentrated acid is one of concentrated sulfuric acid, concentrated hydrochloric acid and concentrated nitric acid, preferably nitric acid; the using amount mL of the concentrated acid can be 48-72 times of the weight of the commercialized KB, and the preferable using amount mL of the concentrated acid is 60 times of the weight of the commercialized KB; the carbon source is one of acetylene black, Super-P, Ketjen black and BP2000, and preferably the Ketjen black; the reflux temperature can be 70-80 ℃, and the reflux time can be 7-8.5 h; the preferred refluxing temperature is 80 ℃, and the refluxing time is 8 h; the temperature of the vacuum drying can be 100-110 ℃, the time of the vacuum drying can be more than 12 hours, and the preferred temperature of the vacuum drying is 110 ℃.
In the step 2), the mass ratio of the carbon source, the nitrogen source and the cobalt source is (1-4): 1; the dosage of the organic solvent can be 20-30 times of the weight of the reaction materials, preferably 25 times of the weight of the reaction materials; the organic solvent may be one selected from anhydrous ethanol, N-dimethylformamide, styrene, acrylic acid, etc., and preferably, anhydrous ethanol.
In the step 3), the time of ultrasonic dispersion can be 30-60 min.
In the step 4), the temperature for heating and stirring can be 60-80 ℃, and is preferably 70 ℃; the stirring speed can be 600-800 r/min, preferably 800 r/min.
In the step 5), the pyrolysis time can be 1-5 h, the pyrolysis temperature can be 600-1000 ℃, and the pyrolysis time is preferably 3h and the pyrolysis temperature is 800 ℃.
The cobalt-nitrogen doped carbon material can be applied to preparation of the all-solid-state lithium-sulfur battery composite positive electrode material as a conductive matrix material.
The specific method for preparing the all-solid-state lithium-sulfur battery composite positive electrode material can be as follows:
1) mixing sublimed sulfur and a cobalt-nitrogen doped carbon material, and then carrying out ball milling to obtain a mixture A;
2) and mixing the sulfide solid electrolyte with the mixture A, and then carrying out ball milling in an inert atmosphere to obtain the all-solid-state lithium-sulfur battery composite positive electrode material.
In the step 1), the size of the cobalt nitrogen doped carbon material is 10-200 nm; the mass ratio of the sublimed sulfur to the cobalt nitrogen doped carbon material can be (40-50): 15-20, and preferably is 50: 15; the ball milling speed of the ball milling is 200-1000 r/min, the ball milling time is 2-6 h, preferably the ball milling speed is 500r/min, and the ball milling time is 4 h.
In step 2), the sulfideThe solid electrolyte comprises 70Li2S-30P2S5、Li7P3S11、β-Li3PS4、Li9.54Si1.74P1.44S11.7Cl0.3、Li10GeP2S12、Li6PS5Cl、Li6PS5Br or the like, preferably Li7P3S11(ii) a The mass ratio of the sulfide solid electrolyte to the mixture A is (55-70): 30-45, preferably 65: 35; the ball milling speed of the ball milling is 200-800 r/min, the ball milling time is 4-8 h, preferably the ball milling speed is 400r/min, and the ball milling time is 6 h; the inert atmosphere may be selected from one of nitrogen, argon, helium, neon, and preferably argon.
The all-solid-state lithium-sulfur battery composite positive electrode material can be applied to preparation of all-solid-state lithium-sulfur batteries.
The method for preparing the all-solid-state lithium-sulfur battery comprises the following steps of:
1) weighing sulfide solid electrolyte powder, placing the sulfide solid electrolyte powder into a polycarbonate tube, and performing cold press molding;
2) weighing the composite positive electrode material of the all-solid-state lithium-sulfur battery, uniformly paving the composite positive electrode material on one side of an electrolyte sheet, and carrying out cold pressing to ensure that the composite positive electrode material is fully contacted;
3) and placing the lithium indium alloy cathode on the other side of the electrolyte sheet for cold pressing to make the lithium indium alloy cathode fully contact with the electrolyte sheet to obtain the all-solid-state lithium-sulfur battery.
In step 1), the sulfide solid electrolyte is 70Li2S-30P2S5、Li7P3S11、β-Li3PS4、Li9.54Si1.74P1.44S11.7Cl0.3、Li10GeP2S12、Li6PS5Cl、Li6PS5One of Br, preferably Li7P3S11。
In the steps 1) and 2), the pressure of the cold pressing is 300-400 MPa, preferably 360 MPa; in the step 3), the pressure of the cold pressing is 150-200 MPa, preferably 180 MPa.
In the step 3), the molar ratio of the metal lithium to the metal indium in the lithium indium alloy is (1-3): 7-9), and preferably 3: 7.
Compared with the prior art, the invention has the beneficial effects that:
1. the cobalt-nitrogen doped carbon material Co prepared by the invention3O4the/Co-N-C has a good core-shell structure, can relieve the volume expansion effect of sulfur to a certain extent, and has good conductivity to promote the electronic conductivity of the sulfur anode material, improve the reversible specific capacity and prolong the cycle life of the all-solid-state lithium sulfur battery.
2. The invention adopts two-step ball milling to realize the close contact and the uniform dispersion of elemental sulfur, the electronic conductive agent and the solid electrolyte, and construct uniform electronic and ion conductive channels for the anode, thereby being beneficial to reducing the interface impedance between the elemental sulfur and the solid electrolyte, reducing the capacity loss of the sulfur anode and improving the utilization rate of the active material of the battery.
3. The invention adopts high-energy ball milling to ensure that the particle size of sublimed sulfur after ball milling reaches the nanometer level, and the operation is simple and convenient.
4. The sulfur composite anode material prepared by the invention is directly used as the anode of the all-solid-state lithium sulfur battery, and the obtained battery can be 50 wt% and 6mg/cm2At a high sulfur content and a high sulfur surface loading, at 0.2mA/cm2The current density is circulated, the specific discharge capacity of the first circle is more than 1200mAh/g, and the capacity retention rate is more than or equal to 90 percent after 30 cycles;
5. the invention adopts solid electrolyte to replace organic liquid electrolyte, so that the shuttle effect of polysulfide is not involved, and the safety problems of combustion, leakage and the like can be solved.
Drawings
Fig. 1 is a TEM image of a cobalt nitrogen doped carbon material prepared in example 4 of the present invention.
FIG. 2 shows that the temperature of the cobalt-nitrogen doped carbon composite sulfur positive electrode of the all-solid-state lithium-sulfur battery prepared in example 4 of the present invention is 30 ℃, and the temperature is 0.2mA/cm2The cycle curve of (2).
FIG. 3 shows a Co-N doped carbon composite sulfur positive electrode prepared in example 4 of the present invention and a Ketjen black composite prepared in comparative example 1The sulfur anode of the all-solid-state lithium sulfur battery is at 30 ℃ and 0.2mA/cm2Comparative charge-discharge curves of (c).
Fig. 4 is a graph comparing the rate performance at 30 ℃ of all-solid-state lithium-sulfur batteries of the cobalt-nitrogen-doped carbon composite sulfur positive electrode prepared in example 4 of the present invention and the ketjen black composite sulfur positive electrode prepared in comparative example 1.
Detailed Description
Preferred and comparative examples are described in detail below with reference to the accompanying drawings.
Example 1
(1) Preparation of cobalt-nitrogen doped carbon material
Acid treatment KB: weighing 2g Ketjen Black (KB), adding 120mL concentrated nitric acid, refluxing in an oil bath at 80 deg.C for 8h, naturally cooling to room temperature, washing with distilled water to remove excess acid, and vacuum drying at 110 deg.C for 12 h.
Preparing a cobalt-nitrogen doped carbon material: adding treated KB, melamine and cobalt acetate (mass ratio is 4: 1) into 50mL of absolute ethyl alcohol, forming homogeneous suspension under the action of ultrasonic dispersion and stirring, then heating to 70 ℃, stirring until the solvent is evaporated to dryness to obtain precursor powder, and pyrolyzing the precursor powder at 800 ℃ for 3h under the argon atmosphere to obtain the target product.
(2) Preparation of sulfur composite cathode material of all-solid-state lithium-sulfur battery
Weighing 0.25g of sublimed sulfur and 0.075g of cobalt-nitrogen doped carbon material in a ball milling tank, adding 35g of ball milling beads for ball milling, and setting ball milling parameters to ball milling for 4 hours at 500rpm to obtain a mixture A; 0.175g of sulfide solid electrolyte Li was added under an argon atmosphere7P3S11And (3) mixing the mixture A, continuing ball milling for 6h under the ball milling parameter set to 400rpm to obtain a sulfur composite anode material, wherein the mass ratio of the active material, the conductive agent and the solid electrolyte in the obtained all-solid-state lithium sulfur battery composite anode material is 50: 15: 35.
(3) Assembled all-solid-state lithium-sulfur battery
Weigh 100mg Li7P3S11Placing the mixture into a polycarbonate tube, performing cold press molding under 360MPa, and weighing a certain mass of all-solid-state lithium-sulfur battery sulfur compositeThe positive electrode material is uniformly spread on one side of the electrolyte sheet and is cold-pressed with the electrolyte under 360MPa to be fully and tightly, and the active substance loading capacity of the sulfur composite positive electrode material of the all-solid-state lithium-sulfur battery is 6mg/cm2(ii) a And (3) placing a lithium indium cathode (the molar ratio of metal lithium to metal indium is 3: 7) on the other side of the electrolyte sheet, carrying out cold pressing at 120MPa to fully contact the lithium indium cathode and the metal indium to obtain the all-solid-state lithium sulfur battery, and placing the battery into a sealed tank filled with inert gas for testing.
Example 2
(1) Preparation of cobalt-nitrogen doped carbon material
Acid treatment KB: weighing 2g Ketjen Black (KB), adding 120mL concentrated nitric acid, refluxing in an oil bath at 80 deg.C for 8h, naturally cooling to room temperature, washing with distilled water to remove excess acid, and vacuum drying at 110 deg.C for 12 h.
Preparing a cobalt-nitrogen doped carbon material: adding treated KB, melamine and cobalt acetate (mass ratio is 4: 2: 1) into 50mL of absolute ethyl alcohol, forming homogeneous suspension under the action of ultrasonic dispersion and stirring, then heating to 70 ℃, stirring until the solvent is evaporated to dryness to obtain precursor powder, and pyrolyzing the precursor powder at 800 ℃ for 3h under the argon atmosphere to obtain the target product.
(2) Preparation of sulfur composite cathode material of all-solid-state lithium-sulfur battery
Weighing 0.25g of sublimed sulfur and 0.075g of cobalt-nitrogen doped carbon material in a ball milling tank, adding 35g of ball milling beads for ball milling, and setting ball milling parameters to ball milling for 4 hours at 500rpm to obtain a mixture A; 0.175g of sulfide solid electrolyte Li was added under an argon atmosphere7P3S11And (3) mixing the mixture A, continuing ball milling for 6h under the ball milling parameter set to 400rpm to obtain a sulfur composite anode material, wherein the mass ratio of the active material, the conductive agent and the solid electrolyte in the obtained all-solid-state lithium sulfur battery composite anode material is 50: 15: 35.
(3) Assembled all-solid-state lithium-sulfur battery
Weigh 100mg Li7P3S11Placing the lithium-sulfur battery anode material into a polycarbonate tube, cold-pressing and molding the lithium-sulfur battery anode material in the polycarbonate tube under 360MPa, weighing a certain mass of the sulfur-sulfur composite anode material, and uniformly spreading the sulfur-sulfur composite anode material on an electrolyte sheetOne side of the sulfur composite anode material is fully and tightly cold-pressed with electrolyte under 360MPa, and the active material loading capacity of the sulfur composite anode material of the all-solid-state lithium-sulfur battery is 6mg/cm2(ii) a And (3) placing a lithium indium cathode (the molar ratio of metal lithium to metal indium is 3: 7) on the other side of the electrolyte sheet, carrying out cold pressing at 120MPa to fully contact the lithium indium cathode and the metal indium to obtain the all-solid-state lithium sulfur battery, and placing the battery into a sealed tank filled with inert gas for testing.
Example 3
(1) Preparation of cobalt-nitrogen doped carbon material
Acid treatment KB: weighing 2g Ketjen Black (KB), adding 120mL concentrated nitric acid, refluxing in an oil bath at 80 deg.C for 8h, naturally cooling to room temperature, washing with distilled water to remove excess acid, and vacuum drying at 110 deg.C for 12 h.
Preparing a cobalt-nitrogen doped carbon material: adding treated KB, melamine and cobalt acetate (mass ratio is 4: 3: 1) into 50mL of absolute ethyl alcohol, forming homogeneous suspension under the action of ultrasonic dispersion and stirring, then heating to 70 ℃, stirring until the solvent is evaporated to dryness to obtain precursor powder, and pyrolyzing the precursor powder at 800 ℃ for 3h under the argon atmosphere to obtain the target product.
(2) Preparation of sulfur composite cathode material of all-solid-state lithium-sulfur battery
Weighing 0.25g of sublimed sulfur and 0.075g of cobalt-nitrogen doped carbon material in a ball milling tank, adding 35g of ball milling beads for ball milling, and setting ball milling parameters to ball milling for 4 hours at 500rpm to obtain a mixture A; 0.175g of sulfide solid electrolyte Li was added under an argon atmosphere7P3S11And (3) mixing the mixture A, continuing ball milling for 6h under the ball milling parameter set to 400rpm to obtain a sulfur composite anode material, wherein the mass ratio of the active material, the conductive agent and the solid electrolyte in the obtained all-solid-state lithium sulfur battery composite anode material is 50: 15: 35.
(3) Assembled all-solid-state lithium-sulfur battery
Weigh 100mg Li7P3S11Placing the lithium-sulfur battery anode material into a polycarbonate tube, carrying out cold press molding under 360MPa, weighing a certain mass of the sulfur composite anode material of the all-solid-state lithium-sulfur battery, uniformly spreading the sulfur composite anode material on one side of an electrolyte sheet, and carrying out cold press on the sulfur composite anode material and the electrolyte under 360MPa until the sulfur composite anode material is fully formedCompact, active material loading capacity of the sulfur composite anode material of the all-solid-state lithium-sulfur battery is 6mg/cm2(ii) a And (3) placing a lithium indium cathode (the molar ratio of metal lithium to metal indium is 3: 7) on the other side of the electrolyte sheet, carrying out cold pressing at 120MPa to fully contact the lithium indium cathode and the metal indium to obtain the all-solid-state lithium sulfur battery, and placing the battery into a sealed tank filled with inert gas for testing.
Example 4
(1) Preparation of cobalt-nitrogen doped carbon material
Acid treatment KB: weighing 2g Ketjen Black (KB), adding 120mL concentrated nitric acid, refluxing in an oil bath at 80 deg.C for 8h, naturally cooling to room temperature, washing with distilled water to remove excess acid, and vacuum drying at 110 deg.C for 12 h.
Preparing a cobalt-nitrogen doped carbon material: adding treated KB, melamine and cobalt acetate (mass ratio is 4: 1) into 50mL of absolute ethyl alcohol, forming homogeneous suspension under the action of ultrasonic dispersion and stirring, then heating to 70 ℃, stirring until the solvent is evaporated to dryness to obtain precursor powder, and pyrolyzing the precursor powder at 800 ℃ for 3h under the argon atmosphere to obtain the target product.
A TEM image of the cobalt nitrogen doped carbon material prepared in example 4 is shown in fig. 1.
(2) Preparation of sulfur composite cathode material of all-solid-state lithium-sulfur battery
Weighing 0.25g of sublimed sulfur and 0.075g of cobalt-nitrogen doped carbon material in a ball milling tank, adding 35g of ball milling beads for ball milling, and setting ball milling parameters to ball milling for 4 hours at 500rpm to obtain a mixture A; 0.175g of sulfide solid electrolyte Li was added under an argon atmosphere7P3S11And (3) mixing the mixture A, continuing ball milling for 6h under the ball milling parameter set to 400rpm to obtain a sulfur composite anode material, wherein the mass ratio of the active material, the conductive agent and the solid electrolyte in the obtained all-solid-state lithium sulfur battery composite anode material is 50: 15: 35.
(3) Assembled all-solid-state lithium-sulfur battery
Weigh 100mg Li7P3S11Placing the lithium-sulfur battery anode material into a polycarbonate tube, cold-pressing and molding the lithium-sulfur battery anode material in the polycarbonate tube under 360MPa, weighing a certain mass of the sulfur-sulfur composite anode material, and uniformly spreading the sulfur-sulfur composite anode material on one electrolyte sheetAnd the active material and the electrolyte are cold-pressed to be fully compact under 360MPa, and the active material loading capacity of the sulfur composite positive electrode material of the all-solid-state lithium-sulfur battery is 6mg/cm2(ii) a And (3) placing a lithium indium cathode (the molar ratio of metal lithium to metal indium is 3: 7) on the other side of the electrolyte sheet, carrying out cold pressing at 120MPa to fully contact the lithium indium cathode and the metal indium to obtain the all-solid-state lithium sulfur battery, and placing the battery into a sealed tank filled with inert gas for testing. The cycle performance of the cell is shown in FIG. 2 at room temperature at 0.2mA/cm2Under the charging and discharging current density, the first discharging specific capacity is 1377mAh/g, and an activation process exists; after 30 times of charge-discharge cycles, the capacity retention rate can still reach 91.2%. FIG. 3 shows the rate capability of the anode material at room temperature, after the activation of the first 20 cycles, the specific discharge capacity is stabilized at over 1200mAh/g, and when the current density is increased to 0.5mA/cm2When the current density is recovered to be low, the specific discharge capacity can reach 1050mAh/g, and the current density is recovered to be 0.2mA/cm2The capacity can be completely recovered, which shows that the rate capability of the material is good.
Comparative example 1
(1) Preparation of sulfur composite cathode material of all-solid-state lithium-sulfur battery
Weighing 0.25g of sublimed sulfur and 0.075g of Keqin black in a ball milling tank, adding 35g of ball milling beads for ball milling, and setting ball milling parameters to ball milling for 4 hours at 500rpm to obtain a mixture A; 0.175g of sulfide solid electrolyte Li was added under an argon atmosphere7P3S11And (3) mixing the mixture A, continuing ball milling for 6h under the ball milling parameter set to 400rpm to obtain a sulfur composite anode material, wherein the mass ratio of the active material, the conductive agent and the solid electrolyte in the obtained all-solid-state lithium sulfur battery composite anode material is 50: 15: 35.
(2) Assembled all-solid-state lithium-sulfur battery
Weigh 100mg Li7P3S11Placing the lithium sulfur battery sulfur composite anode material into a polycarbonate tube for cold press molding under 360MPa, weighing a certain mass of the all-solid-state lithium sulfur battery sulfur composite anode material, uniformly spreading the material on one side of an electrolyte sheet, and cold pressing the material and the electrolyte under 360MPa till the material is fully compact, wherein the active material loading capacity of the all-solid-state lithium sulfur battery sulfur composite anode material is 6mg/cm2(ii) a Adding lithium indiumAnd placing the negative electrode (the molar ratio of the metal lithium to the metal indium is 3: 7) on the other side of the electrolyte sheet, performing cold pressing at 120MPa to fully contact the negative electrode and the electrolyte sheet to obtain the all-solid-state lithium-sulfur battery, and placing the battery into a sealed tank filled with inert gas for testing. At 30 ℃ 0.2mA/cm2And after charge and discharge circulation is carried out, the specific discharge capacity of the first circle is 1085mAh/g, the specific charge capacity of the first circle is only 395mAh/g, and as can be seen from the figure 3, the electrochemical performance is obviously lower than that of the embodiment 4. And rate performance was tested at room temperature, fig. 4 is a graph comparing the rate performance at 30 ℃ of all solid-state lithium sulfur batteries of the cobalt nitrogen-doped carbon composite sulfur positive electrode prepared in example 4 of the present invention and the ketjen black composite sulfur positive electrode prepared in comparative example 1, and it can be seen that the rate performance of comparative example 1 is also significantly worse than that of example 4.
While the invention has been described with reference to specific preferred embodiments and comparative embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the invention.
Claims (10)
1. A Co-N doped carbon material is prepared from carbon source, nitrogen source and Co source through dispersing in organic solvent, ultrasonic stirring, and high-temp sintering3O4/Co-N-C。
2. A preparation method of a cobalt-nitrogen doped carbon material is characterized by comprising the following steps:
1) acid treatment of the carbon source; carrying out oil bath reflux treatment on the carbon source by using concentrated acid, cooling to room temperature, removing residual acid, and carrying out vacuum drying;
2) preparing materials; adding a nitrogen source, a cobalt source and the acid-treated carbon source in the step 1) into an organic solvent;
3) ultrasonic dispersion; step 2), the ingredients form a homogeneous suspension under the action of ultrasonic dispersion;
4) drying; heating and stirring the homogeneous suspension obtained in the step 3) until the solvent is completely evaporated to dryness to obtain precursor powder;
5) pyrolyzing; pyrolyzing the precursor powder obtained in the step 4) at high temperature in an inert atmosphere to obtain a black powder sample, namely the cobalt-nitrogen doped carbon material.
3. The method according to claim 2, wherein in step 1), the concentrated acid is one of concentrated sulfuric acid, concentrated hydrochloric acid, and concentrated nitric acid; the using amount mL of the concentrated acid is 48-72 times of the weight mL/g of the commercialized KB; the carbon source is one of acetylene black, Super-P, Keqin black and BP 2000; the reflux temperature can be 70-80 ℃, and the reflux time can be 7-8.5 h; the temperature of the vacuum drying can be 100-110 ℃, and the time of the vacuum drying can be more than 12 h.
4. The method of claim 2, wherein in step 2), the mass ratio of the carbon source, the nitrogen source, and the cobalt source is (1-4): 1; the dosage of the organic solvent can be 20-30 times of the weight of the reaction materials (mL/g); the organic solvent can be one selected from absolute ethyl alcohol, N-dimethylformamide, styrene and acrylic acid.
5. The method for preparing a cobalt-nitrogen doped carbon material according to claim 2, wherein in the step 3), the ultrasonic dispersion time is 30-60 min;
in the step 4), the temperature for heating and stirring is 60-80 ℃; the stirring speed is 600-800 r/min;
in the step 5), the pyrolysis time is 1-5 h, and the pyrolysis temperature is 600-1000 ℃.
6. The cobalt-nitrogen doped carbon material as claimed in claim 1 is used as a conductive matrix material in the preparation of a composite cathode material of an all-solid-state lithium-sulfur battery.
7. The application of the composite cathode material of the all-solid-state lithium-sulfur battery according to claim 6, wherein the specific method for preparing the composite cathode material of the all-solid-state lithium-sulfur battery comprises the following steps:
1) mixing sublimed sulfur and a cobalt-nitrogen doped carbon material, and then carrying out ball milling to obtain a mixture A;
2) and mixing the sulfide solid electrolyte with the mixture A, and then carrying out ball milling in an inert atmosphere to obtain the all-solid-state lithium-sulfur battery composite positive electrode material.
8. The use of claim 7, wherein in step 1), the cobalt nitrogen doped carbon material has a size of 10 to 200 nm; the mass ratio of the sublimed sulfur to the cobalt nitrogen doped carbon material can be (40-50): 15-20, and preferably is 50: 15; the ball milling speed of the ball milling is 200-1000 r/min, the ball milling time is 2-6 h, preferably the ball milling speed is 500r/min, and the ball milling time is 4 h;
in step 2), the sulfide solid state electrolyte includes 70Li2S-30P2S5、Li7P3S11、β-Li3PS4、Li9.54Si1.74P1.44S11.7Cl0.3、Li10GeP2S12、Li6PS5Cl、Li6PS5Br or the like, preferably Li7P3S11(ii) a The mass ratio of the sulfide solid electrolyte to the mixture A is (55-70): 30-45, preferably 65: 35; the ball milling speed of the ball milling is 200-800 r/min, the ball milling time is 4-8 h, preferably the ball milling speed is 400r/min, and the ball milling time is 6 h; the inert atmosphere may be selected from one of nitrogen, argon, helium, neon, and preferably argon.
9. The application of the composite cathode material of the all-solid-state lithium-sulfur battery in the preparation of the all-solid-state lithium-sulfur battery comprises the following steps:
1) weighing sulfide solid electrolyte powder, placing the sulfide solid electrolyte powder into a polycarbonate tube, and performing cold press molding;
2) weighing the composite positive electrode material of the all-solid-state lithium-sulfur battery, uniformly paving the composite positive electrode material on one side of an electrolyte sheet, and carrying out cold pressing to ensure that the composite positive electrode material is fully contacted;
3) and placing the lithium indium alloy cathode on the other side of the electrolyte sheet for cold pressing to make the lithium indium alloy cathode fully contact with the electrolyte sheet to obtain the all-solid-state lithium-sulfur battery.
10. The use according to claim 9, wherein in step 1) the sulfide solid electrolyte is 70Li2S-30P2S5、Li7P3S11、β-Li3PS4、Li9.54Si1.74P1.44S11.7Cl0.3、Li10GeP2S12、Li6PS5Cl、Li6PS5One kind of Br;
in the steps 1) and 2), the pressure of the cold pressing is 300-400 MPa, preferably 360 MPa; in the step 3), the pressure of the cold pressing is 150-200 MPa;
in the step 3), the molar ratio of the metal lithium to the metal indium in the lithium indium alloy is (1-3): 7-9.
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