CN104993136A - Preparation method of porous lithium ion battery positive composite material lithium vanadium phosphate/carbon - Google Patents
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Abstract
A preparation method of a porous lithium ion battery positive composite material lithium vanadium phosphate/carbon mainly adopts CH3COOLi.2H2O, NH4VO3, C2H2O4.2H2O, NH4H2PO4 and citric acid as raw materials, and comprises the following steps: preparing blue precursor gel of Li3V2(PO4)3/C through adopting a sol-gel process, carrying out vacuum drying, grinding to obtain a powdery blue precursor, dissolving the powdery precursor in an ethanol-water mixed solution as a solvent to obtain a precursor solution, adding the precursor solution to a self-made monodispersed polyacrylamide (PAM) microsphere colloid crystal template with the particle size of about 500nm in a dropwise manner, carrying out vacuum pumping filtration until the template is fully infiltrated, and carrying out vacuum drying and temperature programmed control calcining to prepare the ordered porous lithium ion battery positive composite material lithium vanadium phosphate/carbon. The water solubility of the template adopted in the invention is good, hydrophilic treatment is omitted, and the prepared porous electrode material has excellent high-rate performance.
Description
Technical field the present invention relates to a kind of preparation method of ordered porous anode composite material of lithium ion battery phosphoric acid vanadium lithium/carbon, belongs to the advanced field of batteries of new forms of energy.
Background technology in recent years, as the phosphoric acid vanadium lithium of anode material for lithium-ion batteries because there is good lithium ionic mobility, higher reversible capacity and can the advantage such as operating voltage, preferably fail safe and causing paying close attention to widely, but the lower electronic conductivity that phosphoric acid vanadium lithium itself is intrinsic and lithium ion diffusion coefficient, make its high rate performance poor, greatly limit its practical application.Being prepared as to address this problem of ordered porous electrode material provides effective method.This is because porous electrode material has the following advantages: electrolyte and electrode material surface can be made to have good contact; Be conducive to the Charger transfer between electrode and electrolyte interface; Reduce the distance of ion diffuse passage; Suppress in cyclic process because of the own structural damage of material that volumetric expansion causes; The conduction mesophase spherule contained in composite porous can improve its conductivity and high rate capability etc.At present, the preparation method of porous electrode material has following several: hydro thermal method, solvent-thermal method, template, self-assembly method.In all preparation methods, template is with the plurality of advantages such as simple, foresight is good and by primary study and development.Colloidal crystal template method is a kind of template prepared highly ordered porous materials and commonly use.This method is that monodisperse spherical polymer is with after periodicity assembling, form colloidal crystal, then take colloidal crystal as template, electrode material presoma is filled in the gap location of colloidal crystal, remove colloidal crystal finally by certain mode thus formed needed for electrode material.The Template Types that current employing colloidal crystal template legal system has sequence porous electrode material is less, be only limitted to poly (methyl methacrylate) micro-sphere and polystyrene microsphere etc., due to the poorly water-soluble of these templates, therefore need to carry out hydrophilic treated to make hydrophily precursor solution infiltrate die clearance preferably.And adopt colloidal crystal template legal system to be only limitted to nitrate for lithium battery anode material lithium source.
Summary of the invention the object of the invention is to the shortcoming for prior art, provides the preparation method of a kind of porous lithium ionic cell positive pole material phosphoric acid vanadium lithium/carbon.The present invention is mainly template with polyacrylamide microsphere, take lithium acetate as lithium source, using ethanol and aqueous mixtures as the solvent of precursor solution, adopts colloidal crystal template legal system to have sequence porous lithium ionic cell positive pole composite material phosphoric acid vanadium lithium/carbon.
Preparation method of the present invention is as follows:
(1) by acrylamide (AM), polyvinylpyrrolidone (PVP), it is in the ethanol water of 50 ~ 80% that azodiisobutyronitrile (AIBN) is dissolved in volume ratio successively, the mass percent that above-mentioned three kinds of compositions account for mixed solution total amount is: acrylamide 10 ~ 20%, polyvinylpyrrolidone 2 ~ 4%, azodiisobutyronitrile 0.02 ~ 0.06%, stirring forms colourless transparent solution after making it dissolve completely, this mixed solution is moved in revolving reaction evaporator, after nitrogen replacement, water-bath temperature control 60 ~ 75 DEG C, react 5 ~ 8h under the condition of rotating speed 50 ~ 80r/min and obtain white " milky " liquid, by the at room temperature sedimentation of white " milky " liquid, shift out supernatant liquid, at room temperature vapor away ethanol water solvent again to dry, obtain single dispersed polyacrylamide (PAM) microballoon colloidal crystal template.
(2) 3 ~ 8g NH is added by every 100mL deionized water
4vO
3, by NH
4vO
3be dissolved in deionized water, water-bath temperature control 35 DEG C, NH in molar ratio
4vO
3: C
2h
2o
42H
2o:CH
3cOOLi2H
2o:NH
4h
2pO
4: citric acid solution=2:6:3:3:2 is successively to above-mentioned NH
4vO
3c is added in solution
2h
2o
42H
2o, CH
3cOOLi2H
2o, NH
4h
2pO
4, citric acid solution, bath temperature was adjusted to 80 DEG C after 30 minutes by magnetic agitation, continue stir, heating, evaporate unnecessary moisture content until formed blue gel, grind after this gel 80 DEG C of vacuumize 10 ~ 14h, obtain blue powder shape Li
3v
2(PO
4)
3the presoma of/C.
(3) be that 40 ~ 70% ethanol waters add the obtained blue Li of 6 ~ 10g above-mentioned steps (2) by every 100ml volume ratio
3v
2(PO
4)
3the ratio of/C precursor powder, by blue Li obtained for above-mentioned steps 2
3v
2(PO
4)
3/ C precursor powder adds and fills in the container of ethanol water, is 35 DEG C, makes it dissolve, form blue precursor solution under magnetic agitation after sealing at bath temperature.
(4) single dispersed polyacrylamide (PAM) the microballoon colloidal crystal template that the ratio dripping 7 ~ 13ml precursor solution in every gram of template gets step (1) obtained is placed on the filter membrane in Buchner funnel, precursor solution obtained for step (3) to be dropped in uniformly in template and vacuum filtration, until template is fully infiltrated by precursor solution.
(5) step (4) is placed in vacuum drying chamber by the template that precursor solution fully infiltrates, 80 DEG C of vacuumize 8h.Take out after being cooled to room temperature.
(6) dried template is placed in the tube furnace Program temperature control calcining being connected with nitrogen.Calcination procedure is as follows: 230 DEG C of calcinings 1h (programming rate 1 ~ 3 DEG C/min), 400 ~ 450 DEG C of calcinings 2 ~ 3h (programming rate 1 ~ 4 DEG C/min), 550 DEG C of calcinings 2 ~ 3h (programming rate 4 DEG C/min), 650 ~ 800 DEG C of calcinings 6 ~ 8h (programming rate 5 DEG C/min).Take out after being cooled to room temperature, grind and obtain ordered porous anode composite material of lithium ion battery Li
3v
2(PO
4)
3/ C.
The present invention compared with prior art tool has the following advantages:
1, template polyacrylamide (PAM) microballoon adopted has water-soluble preferably, and precursor solution can infiltrate in the gap of template microsphere well, without the need to carrying out hydrophilic treated.
2, adopt this template, breach the limitation that the lithium source adopting colloidal crystal template legal system to have sequence porous lithium ionic cell positive pole composite material is at present only nitrate.
3, prepared ordered porous electrode composite material phosphoric acid vanadium lithium/carbon is used for the high rate performance that lithium ion cell positive has good cyclical stability and excellence, when charging/discharging voltage is 3.0-4.8V, under 15C current density discharge and recharge condition, first discharge specific capacity is 125.1mAh/g.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the single dispersed polyacrylamide microsphere that the embodiment of the present invention 1 obtains.
Fig. 2 is the XRD figure of ordered porous anode composite material of lithium ion battery phosphoric acid vanadium lithium/carbon that the embodiment of the present invention 1 obtains.
Fig. 3 is the SEM figure of ordered porous anode composite material of lithium ion battery phosphoric acid vanadium lithium/carbon that the embodiment of the present invention 1 obtains.
Fig. 4 is the high rate performance figure of ordered porous anode composite material of lithium ion battery phosphoric acid vanadium lithium/carbon that the embodiment of the present invention 1 obtains.
Embodiment
Embodiment 1
Volume ratio 10g acrylamide (AM), 2g polyvinylpyrrolidone (PVP), 0.02g azodiisobutyronitrile (AIBN) being dissolved in successively 88mL is in the ethanol water of 60%, stirring makes it dissolve formation colourless transparent solution completely, this mixed solution is moved in revolving reaction evaporator, after nitrogen replacement, water-bath temperature control 70 DEG C, react 6h under the reaction condition of rotating speed 70r/min and obtain white " milky " liquid.By the at room temperature sedimentation of white " milky " liquid, shift out supernatant liquid, more at room temperature solvent flashing, to dry, obtains single dispersed polyacrylamide (PAM) the microballoon colloidal crystal that particle diameter is about about 500nm, as shown in Figure 1.
By 2.363g NH
4vO
3be dissolved in 50ml deionized water, water-bath temperature control 35 DEG C, adds 7.962gC successively
2h
2o
42H
2o, 3.091g CH
3cOOLi2H
2o, 3.468g NH
4h
2pO
4, 4.224g citric acid solution, bath temperature was adjusted to 80 DEG C after 30 minutes by magnetic agitation, continue stir, heating, evaporate unnecessary moisture content until formed blue gel, grind after this gel 80 DEG C of vacuumize 12h, obtain blue powder shape Li
3v
2(PO
4)
3the presoma of/C.
Above-mentioned for 1.5g blue precursor powder is added to fill 15mL volume ratio be in the round-bottomed flask of the ethanol water of 60%, be 35 DEG C at bath temperature after sealing, make it dissolve under magnetic agitation condition, form blue precursor solution.
Getting the above-mentioned single dispersed polyacrylamide of 2g (PAM) microballoon colloidal crystal template is placed on the filter membrane in Buchner funnel, the 15mL precursor solution of above-mentioned preparation to be dropped in uniformly in template and vacuum filtration, until template is fully infiltrated by precursor solution.
The template fully infiltrated by precursor solution is placed in vacuum drying chamber, 80 DEG C of vacuumize 8h.Take out after being cooled to room temperature.
Dried template is placed in the tube furnace Program temperature control calcining being connected with nitrogen.Calcination procedure is as follows: 230 DEG C of calcinings 1h (programming rate 1 DEG C/min), 440 DEG C of calcinings 3h (programming rate 1 DEG C/min), 550 DEG C of calcinings 2h (programming rate 4 DEG C/min), 750 DEG C of calcinings 8h (programming rate 5 DEG C/min).Take out after being cooled to room temperature, grind and obtain the ordered porous anode composite material of lithium ion battery Li of aperture about 400 ~ 500nm
3v
2(PO
4)
3/ C.
As shown in Figure 2, the ordered porous Li of preparation can be found out
3v
2(PO
4)
3/ C is monocline, without dephasign.Observed by SEM and find, electrode material surface is dispersed with the pore structure that aperture is about 400 ~ 500nm uniformly, as shown in Figure 3.
Test as shown in Figure 4 the high rate performance of ordered porous Li3V2 (PO4) 3/C of preparation, test condition is as follows: make negative pole with lithium metal, and acetylene black makes conductive agent, and Kynoar makes binding agent, and electrolyte is for containing 1mol/LLiPF
6dMC+EC (volume ratio DMC:EC=1:1), barrier film is polypropylene Celgard 2300.The ordered porous Li that the embodiment of the present invention 1 is prepared
3v
2(PO
4)
3/ C is assembled into column half-cell in glove box.Test voltage scope is 3.0 ~ 4.8V, battery when 15C first discharge capacity be 125.1mAh/g.
Embodiment 2
It is in the ethanol water of 70% that 15g acrylamide (AM), 4g polyvinylpyrrolidone (PVP), 0.04g azodiisobutyronitrile (AIBN) are dissolved in 81mL volume ratio successively, stirring makes it dissolve formation colourless transparent solution completely, this solution is moved in revolving reaction evaporator, after nitrogen replacement, water-bath temperature control 60 DEG C, react 8h under the reaction condition of rotating speed 80r/min and obtain white " milky " liquid.By the at room temperature sedimentation of white " milky " liquid, shift out supernatant liquid, more at room temperature solvent flashing, to dry, obtains single dispersed polyacrylamide (PAM) the microballoon colloidal crystal that particle diameter is about about 600nm ~ 800nm.
By 2.363g NH
4vO
3be dissolved in 60ml deionized water, water-bath temperature control 35 DEG C, adds 7.962gC successively
2h
2o
42H
2o, 3.091g CH
3cOOLi2H
2o, 3.468g NH
4h
2pO
4, 4.224g citric acid solution, bath temperature was adjusted to 80 DEG C after 30 minutes by magnetic agitation, continue stir, heating, evaporate unnecessary moisture content until formed blue gel, grind after this gel 80 DEG C of vacuumize 10h, obtain blue powder shape Li
3v
2(PO
4)
3the presoma of/C.
Above-mentioned for 1.5g blue precursor powder is added to fill 20mL volume ratio be in the round-bottomed flask of the ethanol water of 50%, be 35 DEG C at bath temperature after sealing, make it dissolve under magnetic agitation condition, form blue precursor solution.
Getting 2.0g single dispersed polyacrylamide (PAM) microballoon colloidal crystal template is placed on the filter membrane in Buchner funnel, the 20mL precursor solution of above-mentioned preparation to be dropped in uniformly in template and vacuum filtration, until template is fully infiltrated by precursor solution.
The template fully infiltrated by precursor solution is placed in vacuum drying chamber, 80 DEG C of vacuumize 8h.Take out after being cooled to room temperature.
Dried template is placed in the tube furnace Program temperature control calcining being connected with nitrogen.Calcination procedure is as follows: 230 DEG C of calcinings 1h (programming rate 2 DEG C/min), 400 DEG C of calcinings 2h (programming rate 2 DEG C/min), 550 DEG C of calcinings 3h (programming rate 4 DEG C/min), 700 DEG C of calcinings 7h (programming rate 5 DEG C/min).Take out after being cooled to room temperature, grind and obtain the ordered porous anode composite material of lithium ion battery Li that aperture is about 500nm ~ 800nm
3v
2(PO
4)
3/ C.By adopt the method identical with embodiment 1 record ordered porous anode composite material of lithium ion battery phosphoric acid vanadium lithium/carbon when 15C first discharge capacity be 115.2mAh/g.
Embodiment 3
It is in the ethanol water of 80% that 20g acrylamide (AM), 4g polyvinylpyrrolidone (PVP), 0.06g azodiisobutyronitrile (AIBN) are dissolved in 76mL volume ratio successively, stirring makes it dissolve formation colourless transparent solution completely, this solution is moved in revolving reaction evaporator, after nitrogen replacement, water-bath temperature control 75 DEG C, react 7h under the reaction condition of rotating speed 60r/min and obtain white " milky " liquid.By the at room temperature sedimentation of white " milky " liquid, shift out supernatant liquid, more at room temperature solvent flashing, to dry, obtains single dispersed polyacrylamide (PAM) the microballoon colloidal crystal of particle diameter about about 0.8 ~ 1.0 μm.
By 2.363g NH
4vO
3be dissolved in 40ml deionized water, water-bath temperature control 35 DEG C, adds 7.962gC successively
2h
2o
42H
2o, 3.091g CH
3cOOLi2H
2o, 3.468g NH
4h
2pO
4, 4.224g citric acid solution, bath temperature was adjusted to 80 DEG C after 30 minutes by magnetic agitation, continue stir, heating, evaporate unnecessary moisture content until formed blue gel, grind after this gel 80 DEG C of vacuumize 14h, obtain blue powder shape Li
3v
2(PO
4)
3the presoma of/C.
Above-mentioned for 1.5g blue precursor powder is added to fill 15mL volume ratio be in the round-bottomed flask of the ethanol water of 40%, be 35 DEG C at bath temperature after sealing, make it dissolve under magnetic agitation condition, form blue precursor solution.
Getting 2g single dispersed polyacrylamide (PAM) microballoon colloidal crystal template is placed on the filter membrane in Buchner funnel, to be dropped in uniformly by the 15mL precursor solution of above-mentioned preparation in template and vacuum filtration, until template is fully infiltrated by precursor solution.
The template fully infiltrated by precursor solution is placed in vacuum drying chamber, 80 DEG C of vacuumize 8h.Take out after being cooled to room temperature.
Dried template is placed in the tube furnace Program temperature control calcining being connected with nitrogen.Calcination procedure is as follows: 230 DEG C of calcinings 1h (programming rate 2 DEG C/min), 450 DEG C of calcinings 3h (programming rate 3 DEG C/min), 550 DEG C of calcinings 3h (programming rate 4 DEG C/min), 800 DEG C of calcinings 6h (programming rate 5 DEG C/min).Take out after being cooled to room temperature, grind and obtain the ordered porous anode composite material of lithium ion battery Li that aperture is about about 1.0 μm
3v
2(PO
4)
3/ C.By adopt the method identical with embodiment 1 record ordered porous anode composite material of lithium ion battery phosphoric acid vanadium lithium/carbon when 15C first discharge capacity be 80.0mAh/g.
Embodiment 4
It is in the ethanol water of 50% that 10g acrylamide (AM), 3g polyvinylpyrrolidone (PVP), 0.03g azodiisobutyronitrile (AIBN) are dissolved in 87mL volume ratio successively, stirring makes it dissolve formation colourless transparent solution completely, this solution is moved in revolving reaction evaporator, after nitrogen replacement, water-bath temperature control 65 DEG C, react 5h under the reaction condition of rotating speed 50r/min and obtain white " milky " liquid.By the at room temperature sedimentation of white " milky " liquid, shift out supernatant liquid, more at room temperature solvent flashing, to dry, obtains single dispersed polyacrylamide (PAM) the microballoon colloidal crystal of particle diameter about about 1 μm.
By 2.363g NH
4vO
3be dissolved in 30ml deionized water, water-bath temperature control 35 DEG C, adds 7.962gC successively
2h
2o
42H
2o, 3.091g CH
3cOOLi2H
2o, 3.468g NH
4h
2pO
4, 4.224g citric acid solution, bath temperature was adjusted to 80 DEG C after 30 minutes by magnetic agitation, continue stir, heating, evaporate unnecessary moisture content until formed blue gel, grind after this gel 80 DEG C of vacuumize 12h, obtain blue powder shape Li
3v
2(PO
4)
3the presoma of/C.
Above-mentioned for 1.5g blue precursor powder is added to fill 25mL volume ratio be in the round-bottomed flask of the ethanol water of 70%, be 35 DEG C at bath temperature after sealing, make it dissolve under magnetic agitation condition, form blue precursor solution.
Getting 2g single dispersed polyacrylamide (PAM) microballoon colloidal crystal template is placed on the filter membrane in Buchner funnel, to be dropped in uniformly by the 25mL precursor solution of above-mentioned preparation in template and vacuum filtration, until template is fully infiltrated by precursor solution.
The template fully infiltrated by precursor solution is placed in vacuum drying chamber, 80 DEG C of vacuumize 8h.Take out after being cooled to room temperature.
Dried template is placed in the tube furnace Program temperature control calcining being connected with nitrogen.Calcination procedure is as follows: 230 DEG C of calcinings 1h (programming rate 3 DEG C/min), 450 DEG C of calcinings 2h (programming rate 4 DEG C/min), 550 DEG C of calcinings 3h (programming rate 4 DEG C/min), 650 DEG C of calcinings 8h (programming rate 5 DEG C/min).Take out after being cooled to room temperature, grind aperture is about the ordered porous anode composite material of lithium ion battery Li of about 1.0 μm
3v
2(PO
4)
3/ C, but hole count is less.By adopt the method identical with embodiment 1 record ordered porous anode composite material of lithium ion battery phosphoric acid vanadium lithium/carbon when 15C first discharge capacity be 50.6mAh/g.
Claims (1)
1. a preparation method for porous lithium ionic cell positive pole composite material phosphoric acid vanadium lithium/carbon, is characterized in that: it comprises the steps:
(1) by acrylamide (AM), polyvinylpyrrolidone (PVP), it is in the ethanol water of 50 ~ 80% that azodiisobutyronitrile (AIBN) is dissolved in volume ratio successively, the mass percent that above-mentioned three kinds of compositions account for mixed solution total amount is: acrylamide 10 ~ 20%, polyvinylpyrrolidone 2 ~ 4%, azodiisobutyronitrile 0.02 ~ 0.06%, stirring forms colourless transparent solution after making it dissolve completely, this mixed solution is moved in revolving reaction evaporator, after nitrogen replacement, water-bath temperature control 60 ~ 75 DEG C, react 5 ~ 8h under the condition of rotating speed 50 ~ 80r/min and obtain white " milky " liquid, by the at room temperature sedimentation of white " milky " liquid, shift out supernatant liquid, at room temperature vapor away ethanol water solvent again to dry, obtain single dispersed polyacrylamide (PAM) microballoon colloidal crystal template,
(2) 3 ~ 8g NH is added by every 100mL deionized water
4vO
3, by NH
4vO
3be dissolved in deionized water, water-bath temperature control 35 DEG C, NH in molar ratio
4vO
3: C
2h
2o
42H
2o:CH
3cOOLi2H
2o:NH
4h
2pO
4: citric acid solution=2:6:3:3:2 is successively to above-mentioned NH
4vO
3c is added in solution
2h
2o
42H
2o, CH
3cOOLi2H
2o, NH
4h
2pO
4, citric acid solution, bath temperature was adjusted to 80 DEG C after 30 minutes by magnetic agitation, continue stir, heating, evaporate unnecessary moisture content until formed blue gel, grind after this gel 80 DEG C of vacuumize 10 ~ 14h, obtain blue powder shape Li
3v
2(PO
4)
3the presoma of/C;
(3) be that 40 ~ 70% ethanol waters add the obtained blue Li of 6 ~ 10g above-mentioned steps (2) by every 100ml volume ratio
3v
2(PO
4)
3the ratio of/C precursor powder, by blue Li obtained for above-mentioned steps 2
3v
2(PO
4)
3/ C precursor powder adds and fills in the container of ethanol water, is 35 DEG C, makes it dissolve, form blue precursor solution under magnetic agitation after sealing at bath temperature;
(4) single dispersed polyacrylamide (PAM) the microballoon colloidal crystal template that the ratio dripping 7 ~ 13ml precursor solution in every gram of template gets step (1) obtained is placed on the filter membrane in Buchner funnel, precursor solution obtained for step (3) to be dropped in uniformly in template and vacuum filtration, until template is fully infiltrated by precursor solution;
(5) be placed in vacuum drying chamber by step (4) by the template that precursor solution fully infiltrates, 80 DEG C of vacuumize 8h, take out after being cooled to room temperature;
(6) dried template is placed in the tube furnace Program temperature control calcining being connected with nitrogen, calcination procedure is as follows: 230 DEG C of calcining 1h, programming rate 1 ~ 3 DEG C/min, 400 ~ 450 DEG C of calcining 2 ~ 3h, programming rate 1 ~ 4 DEG C/min, 550 DEG C of calcining 2 ~ 3h, programming rate 4 DEG C/min, 650 ~ 800 DEG C of calcining 6 ~ 8h, programming rate 5 DEG C/min, takes out after being cooled to room temperature, grinds and obtain ordered porous anode composite material of lithium ion battery Li
3v
2(PO
4)
3/ C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106935821A (en) * | 2017-03-16 | 2017-07-07 | 湖南工业大学 | A kind of phosphoric acid vanadium lithium composite positive pole with porous foam and preparation method thereof |
| CN107364893A (en) * | 2017-06-29 | 2017-11-21 | 宁波吉电鑫新材料科技有限公司 | A kind of templated synthesis perovskite lithium ion battery negative material and preparation method thereof |
| CN114256446A (en) * | 2020-09-23 | 2022-03-29 | 湖南农业大学 | Polyanion type positive electrode material and preparation method and application thereof |
| CN114890480A (en) * | 2022-03-18 | 2022-08-12 | 常州大学 | Preparation method of manganese-cobalt-nickel-carbonate precursor based on high-molecular microsphere template and lithium-rich manganese-based positive electrode material |
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| WO2012023904A1 (en) * | 2010-08-20 | 2012-02-23 | National University Of Singapore | Mesoporous metal phosphate materials for energy storage application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106935821A (en) * | 2017-03-16 | 2017-07-07 | 湖南工业大学 | A kind of phosphoric acid vanadium lithium composite positive pole with porous foam and preparation method thereof |
| CN106935821B (en) * | 2017-03-16 | 2019-12-06 | 湖南工业大学 | lithium vanadium phosphate composite cathode material with porous foam and preparation method thereof |
| CN107364893A (en) * | 2017-06-29 | 2017-11-21 | 宁波吉电鑫新材料科技有限公司 | A kind of templated synthesis perovskite lithium ion battery negative material and preparation method thereof |
| CN114256446A (en) * | 2020-09-23 | 2022-03-29 | 湖南农业大学 | Polyanion type positive electrode material and preparation method and application thereof |
| CN114890480A (en) * | 2022-03-18 | 2022-08-12 | 常州大学 | Preparation method of manganese-cobalt-nickel-carbonate precursor based on high-molecular microsphere template and lithium-rich manganese-based positive electrode material |
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