CN110237863A - A kind of preparation method and applications of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material - Google Patents

A kind of preparation method and applications of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material Download PDF

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CN110237863A
CN110237863A CN201910538493.7A CN201910538493A CN110237863A CN 110237863 A CN110237863 A CN 110237863A CN 201910538493 A CN201910538493 A CN 201910538493A CN 110237863 A CN110237863 A CN 110237863A
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pomace
dimensional porous
product
carbon
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许占位
关伟伟
马冲
付豪
李康
赵怡星
孔硌
黄剑锋
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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Abstract

The present invention proposes a kind of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material preparation method and applications, using phthalic anhydride, cobalt chloride hexahydrate, pomace carbon and urea as raw material, ammonium molybdate is catalyst, it puts solid-phase sintering in Muffle furnace after grinding uniformly in glass mortar into and obtains three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material, specific surface area is high, three-dimensional open-framework abundant and surface carboxylation functional group can increase ion activation surface area, accelerate electron-transport；It is used to prepare battery anode slice with three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material, interface contact resistance can be reduced, finally effectively improve the electrochemistry of lithium thionyl chloride cell；This method has many advantages, such as that preparation process is simple, at low cost, preparation condition is easily controllable, synthesis cycle is short, constituent is uniform.

Description

A kind of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material Preparation method and applications
Technical field
The present invention relates to technical field of lithium batteries more particularly to a kind of three-dimensional porous pomace carbon to support Cobalt Phthalocyanine lithium-thionyl acyl The preparation method and applications of chlorine cell catalyst material.
Background technique
Lithium battery is divided into lithium primary cell and lithium secondary battery.Lithium primary cell is also referred to as lithium primary battery, can with continuous discharge, Can be with intermittent discharge, once electric energy exhausts just cannot use again, it is close in power density, energy compared with traditional electrochmical power source Degree, specific capacity etc. have very big advantage；Wherein lithium thionyl chloride cell is to compare energy in current lithium primary cell practical application One of highest battery is measured, because it is high with discharge voltage and discharge curve is steady, open-circuit voltage 3.65V, high-energy-density, high ratio The advantages that power, obtains in the occasion that number, household electrical appliances, microelectronics, communication, medical product etc. require electrochmical power source output energy high It is widely applied；However the battery, during storage, the lithium of cathode spontaneous can be reacted with SOCl2 generates LiCl passivating film, the film Positive and negative anodes can be obstructed directly to contact, prevent the further progress of reaction, play isolation protective effect, but in electric discharge, with The thickness of the increase of time, LiCl passivating film gradually increases, and becomes very fine and close, Li+ is caused to be difficult to pass through, and the internal resistance of cell increases, Limitation battery continues to discharge, and in response to this problem, researcher starts the reduction reaction place from SOCl2, carbon positive electrode sets about solving Certainly, it focuses on and suitable effective catalyst is added thereto to improve lithium thionyl chloride cell chemical property.
Transition Metal Phthalocyanine and derivative have conjugated structure, while having electron and nucleophobic characteristic concurrently, And SOCl2With electrophilicity, so, Transition Metal Phthalocyanine and derivative are a kind of excellent of lithium thionyl chloride cell Catalyst, our seminars are verified after positive electrode of lithium thionyl chloride battery is embedded in metal phthalocyanine MPc, by changing electrode table The consistency of face LiCl film changes internal resistance, improves output voltage；There are also researchers to be spread out by microwave method synthetic phthalocyanine Biological MPcOc, which is added in electrolyte, substantially reduces the reaction time, and capacity increases 19.34-55.64%.Based on cyclic voltammetric Method measurement, proposes the function of electrode surface and reaction mechanism.
Transition Metal Phthalocyanine and derivant material are in block structure, are unfavorable for effective infiltration of electronics and electrolyte Thoroughly, the problems such as secondly bad because of its electric conductivity, cause the catalytic performance of material limited, carbon material itself is a kind of catalysis material, It can also be used as carrier, introducing carbon material not only can be used as carrier supported Transition Metal Phthalocyanine and derivative, but also can mention The electronic conduction ability of high catalytic material mostly uses carbon nanotube or graphene to support Transition Metal Phthalocyanine and spread out at present Biology, inductive formation nm-class catalyst improve the electronic conduction ability of catalysis material while sufficiently exposing active site, but It is that experiment discovery carbon nanotube or graphene may be mismatched with the structure of the carbon positive electrode acetylene black of lithium thionyl chloride cell, Phenomena such as plug-hole, winding can be generated, to have an adverse effect to battery.
Summary of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of three-dimensional porous pomace carbon to support The preparation method and applications of Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material can effectively improve cell reaction rate, generate Sparse LiCl film, reduces the internal resistance of battery, improves the average discharge volt and battery capacity of battery, has and is produced into The advantages that this is low, method is simple and easy to control.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of preparation method of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material, specific steps It is as follows:
Step 1: the preparation of three-dimensional porous pomace carbon
(1) 0.5g~1.5g pomace and 0.01g~0.1g potassium hydroxide are taken, kettle in polytetrafluoroethylene (PTFE) is added separately to In, the deionized water of 50ml~80ml is then added, after mixing, the outer kettle of installation hydro-thermal；
(2) kettle outside hydro-thermal is put into blast dry oven, keeps the temperature 10 hours~24 hours at 120 DEG C~200 DEG C, obtains To precast body A；
(3) it after temperature drops to room temperature, takes out precast body A and pours into beaker, be placed on magnetic stirring apparatus, 100 DEG C~120 At DEG C, stirring is evaporated to moisture, becomes thick, is stopped heating, is obtained product B, be then placed in air dry oven, at 60 DEG C At~80 DEG C, it is dried to drying, obtains product C；
(4) product C is put into dual temperature horizontal tube furnace, in the case where heating rate is 1 DEG C~10 DEG C/min, is warming up to 400 DEG C~600 DEG C, 1 hour~4 hours are kept the temperature, makes its carbonization, is then washed at least 3 times suction filtrations of deionized water and dehydrated alcohol It washs, obtains product D and pour into beaker；
(5) it is 10%~30% nitric acid solution to product D is totally submerged that mass fraction is poured into beaker, and it is small to impregnate 8 When~12 hours, to the surface product D carry out carboxylated processing, then washed with deionized water and dehydrated alcohol it is constant to pH value, After suction filtration, at 60 DEG C~80 DEG C, it is dried to drying, obtains three-dimensional porous pomace carbon；
Step 2: the preparation of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material
(1) the three-dimensional porous pomace carbon of 0.1g~1.2g phthalic anhydride and the preparation of 0.01g~0.15g step 1 is weighed It is uniformly mixed in glass mortar；
(2) 0.1g~2.4g urea, 0.01g~0.24g ammonium molybdate, 0.05g~1.4g cobalt chloride hexahydrate is taken to be added to It is put into crucible after being fully ground in above-mentioned mortar, is sintered in Muffle furnace, with 1 DEG C~10 DEG C min-1Speed heating, from Room temperature, which rises, is warming up to 100 DEG C~170 DEG C, keeps the temperature 0.1 hour~1.5 hours；Again with 1 DEG C~10 DEG C min-1Speed be warming up to 220 DEG C~450 DEG C, keep the temperature 1.5 hours~3 hours；
(3) product obtained was first changed water with ultrapure water 10 hours~24 hours and cleaned 8~10 times by cooled to room temperature Afterwards, it filtered, cleaned at least 3 times respectively using deionized water and dehydrated alcohol and is dry to get three-dimensional porous pomace carbon support phthalein Cyanines cobalt lithium thionyl chloride cell catalysis material.
A kind of application of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material, is used to prepare battery Positive plate, specific steps are as follows:
(a) it weighs the acetylene black of 0.1g~0.8g and weighs the three-dimensional porous fruit that the acetylene black quality being added is 4%~8% Slag carbon supports Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material, in mortar after mixing, the PTFE of 0.01g~0.1g is added Lotion, and the deionized water of 1g~4g is added thereto, after being ground to paste, 120 DEG C~180 DEG C guarantors in blast dry oven It is 10 hours~24 hours warm, it is taken out after last cooled to room temperature, obtains product E；
(b) by product E with dehydrated alcohol steep 0.5 hour~2 hours, then use extrinsion pressing, be rolled into a thickness of The film of 0.7mm~1mm is put into 60 DEG C~80 DEG C of baking oven later and keeps the temperature 8 hours~12 hours；
(c) electrode slice that diameter is 12mm is washed into after drying, as lithium primary battery positive plate；Electrode slice size can It is adjusted according to practical application.
The present invention uses phthalic anhydride, cobalt chloride hexahydrate, pomace carbon and urea for raw material, and ammonium molybdate is catalysis Agent puts a step in Muffle furnace into and is heat-treated to obtain three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium after uniformly grinding in glass mortar Thionyl chloride battery catalysis material；It is simple and easy to control with method, the advantages such as production cost is low；Three-dimensional porous pomace carbon presents three-dimensional Reticulated porous structures, as the backing material of Cobalt Phthalocyanine, inductive formation nm-class catalyst can sufficiently expose active sites Electric conductivity is improved while point, and is conducive to react the transfer of electronics using the synergistic effect of the two, improves the catalysis of material Activity and reaction rate, so as to improve close with the average discharge volt, battery capacity and energy that improve lithium/thinly chloride battery Degree, be widely used prospect；The present invention uses solid sintering technology, relative to solwution method, solid sintering technology preparation side Method is simple, and process is easily-controllable, short preparation period, and the repeatability of product is high, and homogeneity is good, at low cost, and reacts without processing The waste liquid and a large amount of by-products generated in journey；Entire preparation process complete mature, is conducive to large-scale production.
Detailed description of the invention
Fig. 1 is the SEM photograph that three-dimensional porous pomace carbon supports Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material.
Fig. 2 is the T-V map that three-dimensional porous pomace carbon supports Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material.
Fig. 3 is the EIS figure that three-dimensional porous pomace carbon supports Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material.
Fig. 4 is that three-dimensional porous pomace carbon supports the SEM figure after the electric discharge of Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material.
Specific embodiment
Present invention is further described in detail combined with specific embodiments below.
Embodiment 1
A kind of preparation method of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material, specific steps Are as follows:
Step 1: the preparation of three-dimensional porous pomace carbon
(1) 1.5g pomace and 0.1g potassium hydroxide are taken, is added separately to then be added in polytetrafluoroethylene (PTFE) in kettle The deionized water of 50ml, after mixing, the outer kettle of installation hydro-thermal；
(2) kettle outside hydro-thermal is put into blast dry oven, keeps the temperature 24 hours at 130 DEG C, obtains precast body A；
(3) it after temperature drops to room temperature, takes out precast body A and pours into beaker, be placed on magnetic stirring apparatus, at 120 DEG C, stir It mixes to moisture and is evaporated, become thick stopping heating, obtain product B, be then placed in air dry oven, at 80 DEG C, be dried to It is dry, obtain product C；
(4) product is placed in dual temperature horizontal tube furnace, at 10 DEG C/min of heating rate, is warming up at 600 DEG C, Heat preservation 3 hours, makes its carbonization, then uses 3 filtering and washings of deionized water and dehydrated alcohol, obtains product D and pour into beaker；
(5) it is 30% nitric acid solution to product D is totally submerged that mass fraction is poured into beaker, is impregnated 10 hours, right The surface product D carry out carboxylated processing, then washed with deionized water and dehydrated alcohol it is constant to pH value, after suction filtration, at 80 DEG C Under, it is dried to drying, obtains three-dimensional porous pomace carbon；
Step 2: the preparation of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material
(1) weigh 0.72g phthalic anhydride and 0.05g step 1 preparation three-dimensional porous pomace carbon in glass mortar It is uniformly mixed；
(2) after taking 0.6g urea, 0.06g ammonium molybdate, 0.6g cobalt chloride hexahydrate to be added to and be fully ground in above-mentioned mortar It is put into crucible, is sintered in Muffle furnace, with 10 DEG C of min-1Speed heating, be warming up to 135 DEG C from room temperature, heat preservation 0.5 Hour；Again with 10 DEG C of min-1Speed be warming up to 260 DEG C, keep the temperature 3 hours；
(3) cooled to room temperature, by product obtained first with changing within ultrapure water 24 hours after water cleans 10 times, using go from Sub- water and dehydrated alcohol are filtered respectively, are cleaned 3 times, dry to get three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium-thionyl chloride electricity Pond catalysis material.
A kind of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material according to made from above step Application, be used to prepare battery anode slice, specific steps are as follows:
(a) it weighs the acetylene black of 0.7g and weighs the three-dimensional porous pomace carbon that the acetylene black quality being added is 8% and support phthalein In mortar after mixing the PTFE emulsion of 0.07g is added in cyanines cobalt lithium thionyl chloride cell catalysis material, and adds thereto The deionized water for entering 4g after being ground to paste, is kept the temperature for 24 hours, after last cooled to room temperature for 150 DEG C in blast dry oven It takes out, obtains product E；
(b) product E dehydrated alcohol is steeped into 30min, then uses extrinsion pressing, is rolled into the film with a thickness of 0.7mm, It is put into 75 DEG C of heat preservation 10h of baking oven later；
(c) it is the electrode slice of 12mm as positive plate that diameter is washed into after drying.
Embodiment 2
A kind of preparation method of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material, specific steps Are as follows:
Step 1: the preparation of three-dimensional porous pomace carbon
(1) 0.5g pomace and 0.01g potassium hydroxide are taken, is added separately to then be added in polytetrafluoroethylene (PTFE) in kettle The deionized water of 50ml, after mixing, the outer kettle of installation hydro-thermal；
(2) kettle outside hydro-thermal is put into blast dry oven, keeps the temperature 20 hours at 175 DEG C, obtains precast body A；
(3) it after temperature drops to room temperature, takes out precast body A and pours into beaker, be placed on magnetic stirring apparatus, at 120 DEG C, stir It mixes to moisture and is evaporated, become thick, stop heating, obtain product B, be then placed in air dry oven, at 80 DEG C, be dried to It is dry, obtain product C；
(4) product C is put into dual temperature horizontal tube furnace, in the case where heating rate is 10 DEG C/min, is warming up to 400 DEG C Under, 4 hours are kept the temperature, its carbonization is made, then with after 3 filtering and washings of deionized water and dehydrated alcohol, product D is obtained and pours into beaker In；
(5) it is 30% nitric acid solution to product D is totally submerged that mass fraction is poured into beaker, is impregnated 10 hours, right The surface product D carry out carboxylated processing, then washed with deionized water and dehydrated alcohol it is constant to pH value, after suction filtration, at 80 DEG C Under, it is dried to drying, obtains three-dimensional porous pomace carbon；
Step 2: the preparation of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material
(1) weigh 1.2g phthalic anhydride and 0.02g step 1 preparation three-dimensional porous pomace carbon in glass mortar It is uniformly mixed；
(2) after taking 0.87g urea, 0.09g ammonium molybdate, 0.9g cobalt chloride hexahydrate to be added to and be fully ground in above-mentioned mortar It is put into crucible, is sintered in Muffle furnace, with 10 DEG C of min-1Speed heating, be warming up to 135 DEG C from room temperature, heat preservation 0.5h；Again with 10 DEG C of min-1Speed be warming up to 280 DEG C, keep the temperature 3h；
(3) cooled to room temperature first changes product obtained after water cleans 8 times with ultrapure water, for 24 hours using deionized water It filters, clean 3 times respectively with dehydrated alcohol, it is dry to be urged to get three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell Change material.
A kind of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material according to made from above step Application, be used to prepare battery anode slice, specific steps are as follows:
(a) it weighs the acetylene black of 0.43g and weighs the three-dimensional porous pomace carbon that the acetylene black quality being added is 5.5% and support In mortar after mixing the PTFE emulsion of 0.05g is added, and thereto in Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material The deionized water of 2.4g is added, after being ground to paste, 150 DEG C of heat preservations for 24 hours, finally naturally cool to room in blast dry oven It is taken out after temperature, obtains product E；
(b) product E dehydrated alcohol is steeped into 30min, then uses extrinsion pressing, is rolled into the film with a thickness of 1mm, it After be put into 75 DEG C of heat preservation 10h of baking oven；
(c) it is the electrode slice of 12mm as positive plate that diameter is washed into after drying.
Embodiment 3
A kind of preparation method of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material, specific steps Are as follows:
Step 1: the preparation of three-dimensional porous pomace carbon
(1) 1g pomace and 0.05g potassium hydroxide are taken, is added separately to then be added in polytetrafluoroethylene (PTFE) in kettle The deionized water of 60ml, after mixing, the outer kettle of installation hydro-thermal；
(2) kettle outside hydro-thermal is put into blast dry oven, keeps the temperature 24 hours at 170 DEG C, obtains precast body A；
(3) it after temperature drops to room temperature, takes out precast body A and pours into beaker, be placed on magnetic stirring apparatus, at 120 DEG C, stir It mixes to moisture and is evaporated, become thick stopping heating, obtain product B, be then placed in air dry oven, at 80 DEG C, be dried to It is dry, obtain product C；
(4) product C is placed in dual temperature horizontal tube furnace, in the case where heating rate is 5 DEG C/min, is warming up to 550 DEG C Under, 3 hours are kept the temperature, its carbonization is made, 3 filtering and washings of deionized water and dehydrated alcohol is then used, obtains product D and pour into beaker In；
(5) it is 20% nitric acid solution to product D is totally submerged that mass fraction is poured into beaker, is impregnated 10 hours, right The surface product D carry out carboxylated processing, then washed with deionized water and dehydrated alcohol it is constant to pH value, after suction filtration, at 80 DEG C Under, it is dried to drying, obtains three-dimensional porous pomace carbon；
Step 2: the preparation of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material
(1) three-dimensional porous pomace carbon made from 0.42g phthalic anhydride and 0.01g step 1 is weighed in glass mortar It is uniformly mixed；
(2) 0.31g urea, 0.028g ammonium molybdate, 0.3g cobalt chloride hexahydrate is taken to be added in above-mentioned mortar and be fully ground After be put into crucible and be sintered in Muffle furnace, with 5 DEG C of min-1Speed heating, be warming up to 130 DEG C from room temperature, keep the temperature 1h； Again with 10 DEG C of min-1Speed be warming up to 250 DEG C, keep the temperature 2.5h；
(3) cooled to room temperature first changes product obtained after water cleans 10 times, using deionization with ultrapure water 15h Water and dehydrated alcohol are filtered respectively, are cleaned 3 times, dry to support Cobalt Phthalocyanine lithium thionyl chloride cell to get three-dimensional porous pomace carbon Catalysis material.
A kind of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material according to made from above step Application, be used to prepare battery anode slice, specific steps are as follows:
(a) it weighs the acetylene black of 0.72g and weighs the three-dimensional porous pomace carbon that the acetylene black quality being added is 5% and support phthalein In mortar after mixing the PTFE emulsion of 0.065g is added in cyanines cobalt lithium thionyl chloride cell catalysis material, and adds thereto The deionized water for entering 3.5g, after being ground to paste, 180 DEG C of heat preservation 20h, last cooled to room temperature in blast dry oven After take out, obtain product E；
(b) product E dehydrated alcohol is steeped into 30min, then uses extrinsion pressing, is rolled into the film with a thickness of 0.8mm, It is put into 75 DEG C of heat preservation 10h of baking oven later；
(c) it is the electrode slice of 12mm as positive plate that diameter is washed into after drying.
Embodiment 4
A kind of preparation method of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material, specific steps Are as follows:
Step 1: the preparation of three-dimensional porous pomace carbon
(1) 1g pomace and 0.04g potassium hydroxide are taken, is added separately to then be added in polytetrafluoroethylene (PTFE) in kettle The deionized water of 50ml, after mixing, the outer kettle of installation hydro-thermal；
(2) kettle outside hydro-thermal is put into blast dry oven, keeps the temperature 24 hours at 160 DEG C, obtains precast body A；
(3) it after temperature drops to room temperature, takes out precast body A and pours into beaker, be placed on magnetic stirring apparatus, at 120 DEG C, stir It mixes to moisture and is evaporated, become thick stopping heating, obtain product B, be then placed in air dry oven, at 80 DEG C, be dried to It is dry, obtain product C；
(4) product C is put into dual temperature horizontal tube furnace, in the case where heating rate is 10 DEG C/min, is warming up to 550 DEG C Under, 2.5 hours are kept the temperature, its carbonization is made, 3 filtering and washings of deionized water and dehydrated alcohol is then used, obtains product D and pour into beaker In；
(5) it is 30% nitric acid solution to product D is totally submerged that mass fraction is poured into beaker, is impregnated 10 hours, right The surface product D carry out carboxylated processing, then washed with deionized water and dehydrated alcohol it is constant to pH value, after suction filtration, at 80 DEG C Under, it is dried to drying, obtains three-dimensional porous pomace carbon；
Step 2: the preparation of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material
(1) three-dimensional porous pomace carbon made from 0.45g phthalic anhydride and 0.015g step 1 is weighed in glass mortar In be uniformly mixed；
(2) 0.27g urea, 0.028g ammonium molybdate, 0.23g cobalt chloride hexahydrate is taken to be added in above-mentioned mortar and be fully ground After be put into crucible, be sintered in Muffle furnace, with 5 DEG C of min-1Speed heating, be warming up to 130 DEG C from room temperature, keep the temperature 1h； Again with 5 DEG C of min-1Speed be warming up to 270 DEG C, keep the temperature 2.5h；
(3) cooled to room temperature first changes product obtained after water cleans 10 times with ultrapure water, for 24 hours using deionization Water and dehydrated alcohol are filtered respectively, are cleaned 3 times, dry to support Cobalt Phthalocyanine lithium thionyl chloride cell to get three-dimensional porous pomace carbon Catalysis material.
A kind of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material according to made from above-mentioned steps Application, be used to prepare battery anode slice, specific steps are as follows:
(a) it weighs the acetylene black of 0.75g and weighs the three-dimensional porous pomace carbon that the acetylene black quality being added is 5% and support phthalein In mortar after mixing the PTFE emulsion of 0.061g is added in cyanines cobalt lithium thionyl chloride cell catalysis material, and adds thereto The deionized water for entering 3.2g after being ground to paste, is kept the temperature for 24 hours for 180 DEG C, last cooled to room temperature in blast dry oven After take out, obtain product E；
(b) product E dehydrated alcohol is steeped into 40min, then uses extrinsion pressing, is rolled into the film with a thickness of 0.7mm, It is put into 75 DEG C of baking oven heat preservations later for 24 hours；
(c) it is the electrode slice of 12mm as positive plate that diameter is washed into after drying.
Embodiment 5
A kind of preparation method of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material, specific steps Are as follows:
Step 1: the preparation of three-dimensional porous pomace carbon
(1) 1g pomace and 0.05g potassium hydroxide are taken, is added separately to then be added in polytetrafluoroethylene (PTFE) in kettle The deionized water of 55ml, after mixing, the outer kettle of installation hydro-thermal；
(2) kettle outside hydro-thermal is put into blast dry oven, keeps the temperature 24 hours at 180 DEG C, obtains precast body A；
(3) it after temperature drops to room temperature, takes out precast body A and pours into beaker, be placed on magnetic stirring apparatus, at 110 DEG C, stir It mixes to moisture and is evaporated, become thick stopping heating, obtain product B, be then placed in air dry oven, at 70 DEG C, be dried to It is dry, obtain product C；
(4) product C is put into dual temperature horizontal tube furnace, in the case where heating rate is 5 DEG C/min, is warming up at 550 DEG C, Heat preservation 2.5 hours, makes its carbonization, then with after 3 filtering and washings of deionized water and dehydrated alcohol, obtains product D and pours into beaker In；
(5) it is 30% nitric acid solution to product D is totally submerged that mass fraction is poured into beaker, is impregnated 10 hours, right The surface product D carry out carboxylated processing, then washed with deionized water and dehydrated alcohol it is constant to pH value, after suction filtration, at 80 DEG C Under, it is dried to drying, obtains three-dimensional porous pomace carbon；
Step 2: the preparation of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material
(1) three-dimensional porous pomace carbon made from 0.48g phthalic anhydride and 0.015g step 1 is weighed in glass mortar In be uniformly mixed；
(2) 0.31g urea, 0.028g ammonium molybdate, 0.303g cobalt chloride hexahydrate is taken to be added in above-mentioned mortar and sufficiently grind It is put into crucible after mill, is sintered in Muffle furnace, with 5 DEG C of min-1Speed heating, be warming up to 135 DEG C from room temperature, heat preservation 1h；Again with 10 DEG C of min-1Speed be warming up to 260 DEG C, keep the temperature 3h；
(3) cooled to room temperature first changes product obtained after water cleans 10 times, using deionization with ultrapure water 12h Water and dehydrated alcohol are filtered respectively, are cleaned 3 times, dry to support Cobalt Phthalocyanine lithium thionyl chloride cell to get three-dimensional porous pomace carbon Catalysis material.
A kind of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material according to made from above-mentioned steps Application, be used to prepare battery anode slice, specific steps are as follows:
(a) it weighs the acetylene black of 0.78g and weighs the three-dimensional porous pomace carbon that the acetylene black quality being added is 4% and support phthalein In mortar after mixing the PTFE emulsion of 0.065g is added in cyanines cobalt lithium thionyl chloride cell catalysis material, and adds thereto The deionized water for entering 3.5g, after being ground to paste, 140 DEG C of heat preservation 20h, last cooled to room temperature in blast dry oven After take out, obtain product E；
(b) product E dehydrated alcohol is steeped into 80min, then uses extrinsion pressing, is rolled into a thickness of 0.75mm's Film is put into 75 DEG C of heat preservation 10h of baking oven later；
(c) it is the electrode slice of 12mm as positive plate that diameter is washed into after drying.
Referring to Fig. 1, the SEM photograph of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material is three-dimensional Porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material is in coarse pored structure, and surface is the little particle of some protrusions With some micropores, be conducive to the specific surface area for improving material.
Referring to fig. 2, the T-V map of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material, this hair The composite material of bright preparation be applied to lithium thionyl chloride cell catalysis material when, show excellent chemical property, i.e., when When permanent 100 Ω of resistance, battery discharge to 2.99V or more duration is up to 10.5min, shows the compound pomace carbon tool of Cobalt Phthalocyanine There are higher average voltage and energy density.
Referring to Fig. 3, the EIS figure of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material, it can be seen that Three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material effectively reduces electricity for lithium thionyl chloride cell Pond internal resistance.
Referring to fig. 4, the SEM after the electric discharge of Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material is supported for three-dimensional porous pomace carbon Figure, material surface is the little particle of protrusion, rather than a thick layer of densification LiCl film.
Embodiment described above is only used to illustrate the technical scheme of the present invention rather than its limitations, although referring to above-mentioned implementation Example describes the invention in detail, it should be understood by those ordinary skilled in the art that: still can be to tool of the invention Body embodiment is modified or replaced equivalently, and any modification without departing from spirit and scope of the invention or is equally replaced It changes, should all cover in scope of the invention as claimed.

Claims (10)

1. a kind of preparation method of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material, feature exist In: comprising the following specific steps
Step 1: the preparation of three-dimensional porous pomace carbon
(1) 0.5g~1.5g pomace and 0.01g~0.1g potassium hydroxide are taken, is added separately in polytetrafluoroethylene (PTFE) in kettle, Then the deionized water of 50ml~80ml is added, after mixing, the outer kettle of installation hydro-thermal；
(2) kettle outside hydro-thermal is put into blast dry oven, keeps the temperature 10 hours~24 hours at 120 DEG C~200 DEG C, obtains pre- Body A processed；
(3) it after temperature drops to room temperature, takes out precast body A and pours into beaker, be placed on magnetic stirring apparatus, at 100 DEG C~120 DEG C Under, stirring be evaporated to moisture, become thick, stop heating, obtain product B, be then placed in air dry oven, 60 DEG C~ At 80 DEG C, it is dried to drying, obtains product C；
(4) product C is put into dual temperature horizontal tube furnace, in the case where heating rate is 1 DEG C~10 DEG C/min, is warming up to 400 DEG C ~600 DEG C, 1 hour~4 hours are kept the temperature, its carbonization is made, then used deionized water and dehydrated alcohol at least 3 filtering and washings, obtain It is poured into beaker to product D；
(5) nitric acid solution that mass fraction is 10%~30% is poured into beaker to product D is totally submerged, impregnate 8 hours~ 12 hours, carboxylated processing is carried out to the surface product D, suction filtration constant to pH value is then washed with deionized water and dehydrated alcohol Afterwards, at 60 DEG C~80 DEG C, it is dried to drying, obtains three-dimensional porous pomace carbon；
Step 2: the preparation of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material
(1) the three-dimensional porous pomace carbon of 0.1g~1.2g phthalic anhydride and the preparation of 0.01g~0.15g step 1 is weighed in glass It is uniformly mixed in glass mortar；
(2) 0.1g~2.4g urea, 0.01g~0.24g ammonium molybdate, 0.05g~1.4g cobalt chloride hexahydrate is taken to be added to above-mentioned It after being fully ground in mortar, is put into crucible and is sintered in Muffle furnace, with 1 DEG C~10 DEG C min-1Speed heating, from room temperature It rises and is warming up to 100 DEG C~170 DEG C, keep the temperature 0.1 hour~1.5 hours；Again with 1 DEG C~10 DEG C min-1Speed be warming up to 220 DEG C ~450 DEG C, keep the temperature 1.5 hours~3 hours；
(3) cooled to room temperature, by product obtained first with changing within ultrapure water 10 hours~24 hours after water cleans 8~10 times, It filtered, cleaned at least 3 times respectively using deionized water and dehydrated alcohol and is dry to get three-dimensional porous pomace carbon support Cobalt Phthalocyanine Lithium thionyl chloride cell catalysis material.
2. a kind of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material according to claim 1 Using, it is characterised in that: it is used to prepare battery anode slice, the specific steps are as follows:
(a) it weighs the acetylene black of 0.1g~0.8g and weighs the three-dimensional porous pomace carbon that the acetylene black quality being added is 4%~8% Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material is supported, in mortar after mixing, the PTFE cream of 0.01g~0.1g is added Liquid, and the deionized water of 1g~4g is added thereto, after being ground to paste, 120 DEG C~180 DEG C heat preservations in blast dry oven It 10 hours~24 hours, takes out after last cooled to room temperature, obtains product E；
(b) product E dehydrated alcohol is steeped 0.5 hour~2 hours, then uses extrinsion pressing, is rolled into a thickness of 0.7mm The film of~1mm is put into 60 DEG C~80 DEG C of baking oven later and keeps the temperature 8 hours~12 hours；
(c) it is the electrode slice of 12mm as lithium primary battery positive plate that diameter is washed into after drying；Electrode slice size can basis Practical application adjustment.
3. a kind of preparation method of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material, feature exist In: specific step is as follows:
Step 1: the preparation of three-dimensional porous pomace carbon
(1) 1.5g pomace and 0.1g potassium hydroxide are taken, is added separately in polytetrafluoroethylene (PTFE) in kettle, is then added 50ml's Deionized water, after mixing, the outer kettle of installation hydro-thermal；
(2) kettle outside hydro-thermal is put into blast dry oven, keeps the temperature 24 hours at 130 DEG C, obtains precast body A；
(3) it after temperature drops to room temperature, takes out precast body A and pours into beaker, be placed on magnetic stirring apparatus, at 120 DEG C, stirring is extremely Moisture is evaporated, and is become thick stopping heating, is obtained product B, be then placed in air dry oven, at 80 DEG C, be dried to drying, Obtain product C；
(4) product is put into dual temperature horizontal tube furnace, at 10 DEG C/min of heating rate, is warming up at 600 DEG C, heat preservation 3 Hour, make its carbonization, then uses 3 filtering and washings of deionized water and dehydrated alcohol, obtain product D and pour into beaker；
(5) it is 30% nitric acid solution to product D is totally submerged that mass fraction is poured into beaker, is impregnated 10 hours, to product D Surface carry out carboxylated processing, then washed with deionized water and dehydrated alcohol it is constant to pH value, after suction filtration, at 80 DEG C, dry To drying, three-dimensional porous pomace carbon is obtained；
Step 2: the preparation of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material
(1) the three-dimensional porous pomace carbon for weighing 0.72g phthalic anhydride and the preparation of 0.05g step 1 mixes in glass mortar Uniformly；
(2) take 0.6g urea, 0.06g ammonium molybdate, 0.6g cobalt chloride hexahydrate be added to be fully ground in above-mentioned mortar after be put into Crucible is sintered in Muffle furnace, with 10 DEG C of min-1Speed heating, be warming up to 135 DEG C from room temperature, keep the temperature 0.5 hour； Again with 10 DEG C of min-1Speed be warming up to 260 DEG C, keep the temperature 3 hours；
(3) cooled to room temperature, by product obtained first with changing for ultrapure water 24 hours after water cleans 10 times, using deionized water It filters, clean 3 times respectively with dehydrated alcohol, it is dry to be urged to get three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell Change material.
4. three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material according to claim 3 is answered With, it is characterised in that: it is used to prepare battery anode slice, specific steps are as follows:
(a) it weighs the acetylene black of 0.7g and weighs the three-dimensional porous pomace carbon that the acetylene black quality being added is 8% and support Cobalt Phthalocyanine In mortar after mixing the PTFE emulsion of 0.07g is added in lithium thionyl chloride cell catalysis material, and 4g is added thereto Deionized water, after being ground to paste, in blast dry oven 150 DEG C heat preservation for 24 hours, taken after last cooled to room temperature Out, product E is obtained；
(b) product E dehydrated alcohol is steeped into 30min, then uses extrinsion pressing, is rolled into the film with a thickness of 0.7mm, later It is put into 75 DEG C of heat preservation 10h of baking oven；
(c) it is the electrode slice of 12mm as positive plate that diameter is washed into after drying.
5. a kind of preparation method of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material, feature exist In: specific step is as follows:
Step 1: the preparation of three-dimensional porous pomace carbon
(1) 0.5g pomace and 0.01g potassium hydroxide are taken, is added separately to that 50ml is then added in polytetrafluoroethylene (PTFE) in kettle Deionized water, after mixing, the outer kettle of installation hydro-thermal；
(2) kettle outside hydro-thermal is put into blast dry oven, keeps the temperature 20 hours at 175 DEG C, obtains precast body A；
(3) it after temperature drops to room temperature, takes out precast body A and pours into beaker, be placed on magnetic stirring apparatus, at 120 DEG C, stirring is extremely Moisture is evaporated, and becomes thick, is stopped heating, is obtained product B, be then placed in air dry oven, at 80 DEG C, be dried to dry It is dry, obtain product C；
(4) product is put into dual temperature horizontal tube furnace, in the case where heating rate is 10 DEG C/min, is warming up at 400 DEG C, keeps the temperature 4 hours, make its carbonization, then uses 3 filtering and washings of deionized water and dehydrated alcohol, obtain product D and pour into beaker；
(5) it is 30% nitric acid solution to product D is totally submerged that mass fraction is poured into beaker, is impregnated 10 hours, to product D Surface carry out carboxylated processing, then washed with deionized water and dehydrated alcohol it is constant to pH value, after suction filtration, at 80 DEG C, dry To drying, three-dimensional porous pomace carbon is obtained；
Step 2: the preparation of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material
(1) the three-dimensional porous pomace carbon for weighing 1.2g phthalic anhydride and the preparation of 0.02g step 1 mixes in glass mortar Uniformly；
(2) take 0.87g urea, 0.09g ammonium molybdate, 0.9g cobalt chloride hexahydrate be added to be fully ground in above-mentioned mortar after be put into Crucible is sintered in Muffle furnace, with 10 DEG C of min-1Speed heating, be warming up to 135 DEG C from room temperature, keep the temperature 0.5h；Again With 10 DEG C of min-1Speed be warming up to 280 DEG C, keep the temperature 3h；
(3) cooled to room temperature first changes product obtained after water cleans 8 times with ultrapure water, for 24 hours using deionized water and nothing Water-ethanol is filtered respectively, is cleaned 3 times, dry to be catalyzed material to get three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell Material.
6. three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material according to claim 5 is answered With, it is characterised in that: it is used to prepare battery anode slice, specific steps are as follows:
(a) it weighs the acetylene black of 0.43g and weighs the three-dimensional porous pomace carbon that the acetylene black quality being added is 5.5% and support phthalocyanine In mortar after mixing the PTFE emulsion of 0.05g is added, and be added thereto in cobalt lithium thionyl chloride cell catalysis material The deionized water of 2.4g after being ground to paste, is kept the temperature for 24 hours, after last cooled to room temperature for 150 DEG C in blast dry oven It takes out, obtains product E；
(b) product E dehydrated alcohol is steeped into 30min, then uses extrinsion pressing, is rolled into the film with a thickness of 1mm, Zhi Houfang Enter 75 DEG C of heat preservation 10h of baking oven；
(c) it is the electrode slice of 12mm as positive plate that diameter is washed into after drying.
7. a kind of preparation method of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material, feature exist In: specific step is as follows:
Step 1: the preparation of three-dimensional porous pomace carbon
(1) 1g pomace and 0.05g potassium hydroxide are taken, is added separately in polytetrafluoroethylene (PTFE) in kettle, is then added 60ml's Deionized water, after mixing, the outer kettle of installation hydro-thermal；
(2) kettle outside hydro-thermal is put into blast dry oven, keeps the temperature 24 hours at 170 DEG C, obtains precast body A；
(3) it after temperature drops to room temperature, takes out precast body A and pours into beaker, be placed on magnetic stirring apparatus, at 120 DEG C, stirring is extremely Moisture is evaporated, and is become thick stopping heating, is obtained product B, be then placed in air dry oven, at 80 DEG C, be dried to drying, Obtain product C；
(4) product C is placed in dual temperature horizontal tube furnace, in the case where heating rate is 5 DEG C/min, is warming up at 550 DEG C, protects Temperature 3 hours, makes its carbonization, then uses 3 filtering and washings of deionized water and dehydrated alcohol, obtains product D and pour into beaker；
(5) it is 20% nitric acid solution to product D is totally submerged that mass fraction is poured into beaker, is impregnated 10 hours, to product D Surface carry out carboxylated processing, then washed with deionized water and dehydrated alcohol it is constant to pH value, after suction filtration, at 80 DEG C, dry To drying, three-dimensional porous pomace carbon is obtained；
Step 2: the preparation of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material
(1) three-dimensional porous pomace carbon made from 0.42g phthalic anhydride and 0.01g step 1 is weighed to mix in glass mortar Uniformly；
(2) it after taking 0.31g urea, 0.028g ammonium molybdate, 0.3g cobalt chloride hexahydrate to be added to and be fully ground in above-mentioned mortar, puts Enter crucible to be sintered in Muffle furnace, Muffle furnace is with 5 DEG C of min-1Speed heating, be warming up to 130 DEG C from room temperature, heat preservation 1h；Again with 10 DEG C of min-1Speed be warming up to 250 DEG C, keep the temperature 2.5h；
(3) cooled to room temperature first changes product obtained after water cleans 10 times with ultrapure water 15h, using deionized water and Dehydrated alcohol is filtered respectively, is cleaned 3 times, dry to get the support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis of three-dimensional porous pomace carbon Material.
8. three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material according to claim 7 is answered With, it is characterised in that: it is used to prepare battery anode slice, specific steps are as follows:
(a) it weighs the acetylene black of 0.72g and weighs the three-dimensional porous pomace carbon that the acetylene black quality being added is 5% and support Cobalt Phthalocyanine In mortar after mixing the PTFE emulsion of 0.065g is added, and be added thereto in lithium thionyl chloride cell catalysis material The deionized water of 3.5g, after being ground to paste, 180 DEG C of heat preservation 20h in blast dry oven, after last cooled to room temperature It takes out, obtains product E；
(b) product E dehydrated alcohol is steeped into 30min, then uses extrinsion pressing, is rolled into the film with a thickness of 0.8mm, later It is put into 75 DEG C of heat preservation 10h of baking oven；
(c) it is the electrode slice of 12mm as positive plate that diameter is washed into after drying.
9. a kind of preparation method of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material, feature exist In: specific step is as follows:
Step 1: the preparation of three-dimensional porous pomace carbon
(1) 1g pomace and 0.04g potassium hydroxide are taken, is added separately in polytetrafluoroethylene (PTFE) in kettle, is then added 50ml's Deionized water, after mixing, the outer kettle of installation hydro-thermal；
(2) kettle outside hydro-thermal is put into blast dry oven, keeps the temperature 24 hours at 160 DEG C, obtains precast body A；
(3) it after temperature drops to room temperature, takes out precast body A and pours into beaker, be placed on magnetic stirring apparatus, at 120 DEG C, stirring is extremely Moisture is evaporated, and is become thick stopping heating, is obtained product B, be then placed in air dry oven, at 80 DEG C, be dried to drying, Obtain product C；
(4) product C is placed in dual temperature horizontal tube furnace, in the case where heating rate is 10 DEG C/min, is warming up at 550 DEG C, Heat preservation 2.5 hours, makes its carbonization, then uses 3 filtering and washings of deionized water and dehydrated alcohol, obtains product D and pour into beaker；
(5) it is 30% nitric acid solution to product D is totally submerged that mass fraction is poured into beaker, is impregnated 10 hours, to product D Surface carry out carboxylated processing, then washed with deionized water and dehydrated alcohol it is constant to pH value, after suction filtration, at 80 DEG C, dry To drying, three-dimensional porous pomace carbon is obtained；
Step 2: the preparation of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material
(1) three-dimensional porous pomace carbon made from 0.45g phthalic anhydride and 0.015g step 1 is weighed to mix in glass mortar It closes uniform；
(2) after taking 0.27g urea, 0.028g ammonium molybdate, 0.23g cobalt chloride hexahydrate to be added to and be fully ground in above-mentioned mortar, It is put into crucible to be sintered in Muffle furnace, with 5 DEG C of min-1Speed heating, be warming up to 130 DEG C from room temperature, keep the temperature 1h；Again With 5 DEG C of min-1Speed be warming up to 270 DEG C, keep the temperature 2.5h；
(3) cooled to room temperature first changes product obtained for 24 hours after water cleans 10 times with ultrapure water, using deionized water and Dehydrated alcohol is filtered respectively, is cleaned 3 times, dry to get the support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis of three-dimensional porous pomace carbon Material.
10. three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material according to claim 9 is answered With, it is characterised in that: it is used to prepare battery anode slice, specific steps are as follows:
(a) it weighs the acetylene black of 0.75g and weighs the three-dimensional porous pomace carbon that the acetylene black quality being added is 5% and support Cobalt Phthalocyanine In mortar after mixing the PTFE emulsion of 0.061g is added, and be added thereto in lithium thionyl chloride cell catalysis material The deionized water of 3.2g after being ground to paste, is kept the temperature for 24 hours, after last cooled to room temperature for 180 DEG C in blast dry oven It takes out, obtains product E；
(b) product E dehydrated alcohol is steeped into 40min, then uses extrinsion pressing, is rolled into the film with a thickness of 0.7mm, later It is put into 75 DEG C of baking oven heat preservations for 24 hours；
(c) it is the electrode slice of 12mm as positive plate that diameter is washed into after drying.
CN201910538493.7A 2019-06-20 2019-06-20 A kind of preparation method and applications of three-dimensional porous pomace carbon support Cobalt Phthalocyanine lithium thionyl chloride cell catalysis material Pending CN110237863A (en)

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CN111063889A (en) * 2019-12-20 2020-04-24 陕西科技大学 Iron phthalocyanine/active carbon Li/SOCl2Preparation method of battery anode catalytic material
CN114100687A (en) * 2021-11-19 2022-03-01 陕西科技大学 Lithium/thionyl chloride battery anode catalytic material CoPc/CuPc and preparation method thereof
CN116459872A (en) * 2023-04-24 2023-07-21 陕西科技大学 Transition metal phthalocyanine/oxidized pomace carbon sulfur fixing material, preparation method, sulfur fixing method and lithium sulfur battery positive electrode material
WO2024140169A1 (en) * 2022-12-29 2024-07-04 蔚来电池科技(安徽)有限公司 Composite material, preparation method, negative pole piece, lithium ion battery and electronic apparatus

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