CN104779378A - Preparation method of cathode material of germanium-mesoporous carbon fiber composite lithium battery - Google Patents
Preparation method of cathode material of germanium-mesoporous carbon fiber composite lithium battery Download PDFInfo
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- CN104779378A CN104779378A CN201510198680.7A CN201510198680A CN104779378A CN 104779378 A CN104779378 A CN 104779378A CN 201510198680 A CN201510198680 A CN 201510198680A CN 104779378 A CN104779378 A CN 104779378A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method of an cathode material of a germanium-mesoporous carbon fiber composite lithium battery. The preparation method comprises the following steps: preparing LN and PAN mixed solutions in different ratios and obtaining LN/PAN composite fibers by virtue of electrostatic spinning, putting the LN/PAN composite fibers into a solvent for etching, and then obtaining carbon fibers of a special mesoporous structure by virtue of pre-oxidation and carbonation; finally, compounding the prepared carbon fibers of the mesoporous structure with GeCl4, and calcining in the mixed atmosphere of N2/H2 in a tubular furnace to obtain the Ge@MCF composite material. According to the preparation method, the mesoporous carbon fibers are prepared by virtue of etching in a waste-based solvent, and the process is green, environment-friendly, and simple; the mesoporous carbon fibers are taken as nano-reactors to prepare the mesoporous carbon fiber composite germanium electrode material; due to the range limitation effect of the mesoporous carbon fibers, the volume change of the germanium electrode material in the lithium implanting/stripping process can be effectively buffered, and high specific capacity and excellent cyclic stability are shown.
Description
Technical field
The invention belongs to a kind of preparing technical field of lithium ion battery negative material, be specifically related to a kind of germanium
-the preparation method of mesoporous carbon fiber composite lithium cell cathode material.
Background technology
In recent years, the performance of high speed development to lithium ion battery of portable electric appts, electric tool and electric vehicle engineering is had higher requirement, and the theoretical specific capacity of traditional graphite cathode material only has 372 mAh g
-1, be difficult to meet the growing requirement to cycle performance of battery and energy density.Therefore, the negative material finding more height ratio capacity and good circulation stability has become an important development direction of field of lithium ion battery material.
The theoretical specific capacity of germanium is up to 1600 mAh g
-1, be about 4 times of graphite-like theoretical capacity, and the diffusion velocity of lithium ion in germanium is fast, can be applicable to high-power high-current equipment, be desirable lithium ion battery negative material.But germanium is but faced with serious volumetric expansion problem in removal lithium embedded process, not only can causes the collapse of electrode material pulverizing and conductive network, and cycle performance sharp-decay can be made.
Mesoporous carbon fiber has larger specific area, unique advantage such as aperture structure, good conductivity, can provide huge reaction interface, fast ion transfer passage.Meanwhile, mesoporous carbon fiber is conducive to the uniform load of active material, the transporting of lithium ion, the diffusion of electrolyte solution and buffering lithium ion, is therefore a kind of good germanium electrode material carrier.But at present about the method preparing mesoporous carbon fiber mainly with soft template method, hard template method or the pore creating materials such as PMMA, ammonium chloride, diisopropyl azodiformate are joined in spinning solution, be main by calcining pore-creating, these methods need to use a large amount of toxic solvent or produce a large amount of harmful exhaust.At present, a kind of method of simple, green, clean synthesising mesoporous carbon fiber is lacked.
Pulp and paper industry needs the cellulose isolating about 1.4 hundred million tons from plant every year, also can obtain the lignin byproduct of about 5,000 ten thousand tons simultaneously.Sodium lignin sulfonate is as the Main By product of sulfite pulping, effectively technology is utilized owing to lacking, mainly be used with low value-added product, or burn with cheap fuel, directly discharge with pulp-making waste-water, cause the waste of this huge biomass resource, also result in serious environmental pollution simultaneously.
The present invention utilizes water-soluble etching method to prepare the matrix of carbon fiber as lithium cell cathode material of special meso-hole structure, and is compounded to form Ge@MCF composite material with germanium source.Utilize the confinement effect of mesoporous carbon fiber, effectively can not only cushion the volumetric expansion of Ge in removal lithium embedded process, and specific capacity and the cyclical stability of lithium cell cathode material can be improved.
Summary of the invention
The object of the invention is to the preparation method of openly a kind of germanium-mesoporous carbon fiber composite lithium cell cathode material.The Ge@MCF combination electrode material prepared by the method has the advantages such as specific capacity is high, good cycling stability.
Adopt technical scheme as follows for realizing object of the present invention:
1, the preparation of mesoporous carbon fiber (MCF): sodium lignin sulfonate (LN) is mixed with polyacrylonitrile (PAN), add dimethyl formamide (DMF) again and be made into certain density spinning solution, obtain LN/PAN composite fibre by electrostatic spinning; The LN/PAN composite fibre obtained is placed in solvent, after etching 12 ~ 48 h, the dry fiber obtaining loose structure in the air dry oven of 70 DEG C; By the fiber of this loose structure in Muffle furnace, 200 ~ 300 DEG C of pre-oxidation 1 ~ 3 h under air atmosphere, in tube furnace under nitrogen atmosphere, adopt progressively temperature-raising method to calcine the fiber after pre-oxidation treatment, calcining heat 500 ~ 800 DEG C, calcination time 1 ~ 3 h; Finally, be warming up to 850 DEG C and adopt CO
2gas activation 1 h, obtains the carbon fiber (MCF) of special meso-hole structure;
The preparation of 2, germanium-mesoporous carbon fiber (Ge@MCF) composite material: get ratio of quality and the number of copies for (3 ~ 8): MCF and GeCl of (2 ~ 7)
4hydro-thermal reaction is carried out in mixing, after the product drying that hydro-thermal reaction obtains, is heated to 400 ~ 700 DEG C, obtains Ge MCF composite material in tube furnace under inert atmosphere with the heating rate of 1.0 ~ 10 DEG C/min;
3, the preparation of lithium ion battery negative material: the Ge@MCF composite material of above-mentioned preparation and acetylene black, Kynoar 75 ~ 80: 10 ~ 15: 5 ~ 10 are prepared burden in mass ratio, be coated in equably on copper sheet after grinding, and dry, obtain lithium ion battery negative material.
In above-mentioned steps,
The concentration 8 ~ 15% of described spinning solution.
The ratio of quality and the number of copies of described LN and PAN is (1 ~ 9): (1 ~ 9).
Described electrospinning conditions refers to voltage 15 ~ 25 kv, receiving range 13 ~ 18 cm, spinning solution plug-flow speed 0.1 ~ 1 ml/h, electrospinning temperature 25 ~ 45 DEG C.
The etching solution of described LN/PAN composite fibre refers to distilled water or aqueous slkali water solvent.
Described progressively temperature-raising method refers to that heating rate is 1 ~ 5 DEG C/min.
Described hydro-thermal reaction refer to mass ratio be 80 ~ 85: 10 ~ 12: 5 ~ 8 MCF and red fuming nitric acid (RFNA), distilled water put into reactor, at 50 ~ 80 DEG C after water-bath 0.5 ~ 1 h with GeCl
4mixing, magnetic agitation 20 min ultrasonic process 30 min.
The drying that described hydro-thermal reaction obtains product refer to product is placed in 10 ~ 30 DEG C magnetic stirring apparatus on be stirred to solvent and volatilize completely, and in the drying box of 50 ~ 100 DEG C dry 2 ~ 8 h.
Described inert atmosphere refers to N
2/ H
2gaseous mixture.
Advantage of the present invention is:
Adopt water solvent etching method, utilize sodium lignin sulfonate to carry out pore-creating, environmental protection, technological operation is simple; The growth of mesoporous carbon fiber to germanium particle that it can be used as nano-reactor to prepare serves certain confinement effect; Ge MCF composite structure is unique, demonstrates high specific capacity and excellent stable circulation performance as lithium ion battery negative material.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the mesoporous carbon fiber (MCF) described in embodiment 1.
Fig. 2 is the N of the mesoporous carbon fiber (MCF) described in embodiment 1
2adsorption and desorption isotherms.
Fig. 3 is the XRD figure of the Ge@MCF composite material described in embodiment 1.
Fig. 4 is the SEM figure of the Ge@MCF composite material described in embodiment 1.
Fig. 5 is the TEM figure of the Ge@MCF composite material described in embodiment 1.
Fig. 6 is the cyclic voltammetry curve of the Ge@MCF composite material described in embodiment 1.
Fig. 7 is that Ge@MCF composite material described in embodiment 1 is at 200 mA g
-1cycle performance figure under current density.
Fig. 8 is that Ge@MCF composite material described in embodiment 1 is at 1 A g
-1long-term cycle performance under current density and coulombic efficiency figure.
Embodiment
In order to better understand the present invention, be now described further by way of example by reference to the accompanying drawings.
In Fig. 6, going back virgin curve has a continuous print reduction peak at about 0.3 V, can belong to Li and Ge and combine formation Li
xthe embedding lithium peak of Ge, the oxidation peak near 0.7 V can belong to lithium ion and deviate from Li in process
xge is converted into the phase transition process of amorphous state Ge, along with proceeding of cyclic voltammetry scan, and Li
xge takes off lithium peak and embedding lithium peak kept stable, illustrates that Ge-MCF combination electrode material has good cycle performance.
In Fig. 7, Ge@MCF composite material is at 200 mA g
-1initial discharge specific capacity under current density is 1444 mAh g
-1, after charge and discharge cycles 50 times, be stabilized in 700 mAh g
-1, demonstrate higher specific capacity.
In Fig. 8, at 1 A g
-1big current under circulation more than 500 times, the specific capacity of Ge@MCF combination electrode material is still up to 389 mAh g
-1, higher than the theoretical specific capacity 372 mAh g of commercialization
-1; Meanwhile, its coulombic efficiency is just up to 99% after the 8th circulation, and show that Ge-MCF composite material maintains high coulombic efficiency in charge and discharge process, reversible capacity is high.
Embodiment 1
1, the preparation of mesoporous carbon fiber (MCF):
Get the LN of 0.994 g, the PAN of 0.426 g and the DMF solvent of 10 ml, after stirring, obtain LN/PAN composite fibre by electrostatic spinning; The LN/PAN composite fibre obtained is placed in after distilled water etches 48 h, the dry fiber obtaining special loose structure in the air dry oven of 70 DEG C; This porous fibrous structure is placed in lower 280 DEG C of process 1 h of Muffle furnace air atmosphere, in tube furnace, is warming up to 700 DEG C and constant temperature 2 h with the heating rate of 1.5 DEG C/min under nitrogen atmosphere; Finally, be heated to 850 DEG C and adopt CO
2gas activation 1 h, obtains the carbon fiber (MCF) of meso-hole structure.Prepared MCF is a kind of fibre structure of mesoporous shape, and its specific area is up to 1070 m
2g
-1, as shown in Figure 1, nitrogen Adsorption and desorption isotherms as shown in Figure 2 for SEM.
2. the preparation of germanium-mesoporous carbon fiber (Ge@MCF) composite material
Get MCF and the red fuming nitric acid (RFNA) of 5 ml, the distilled water of 5 ml of 50 mg, load in polytetrafluoroethyllining lining, hydro-thermal reaction 60 min at 60 DEG C, then centrifugal, washing; The GeCl of MCF and 3 ml obtained will be washed
4, 10 ml absolute ethyl alcohol mix, magnetic agitation 20 min ultrasonic 30 min, obtain the MCF-GeCl mixed
4solution; By MCF-GeCl
4the magnetic stirring apparatus that mixed solution is placed in 18 ~ 26 DEG C is stirred to solvent volatilize completely, obtains MCF@GeCl
4composite material.
3. the preparation of lithium ion battery negative material
By MCF@GeCl obtained above
4composite material in tube furnace, N
2/ H
2300 DEG C are heated to the heating rate of 2.0 DEG C/min under mixed atmosphere, then 600 DEG C are heated to and constant temperature 3 h with the heating rate of 1.0 DEG C/min, obtain the Ge@MCF composite material of special construction, the uniform load of Ge simple substance, on MCF, defines a kind of chain pearlitic texture.As shown in Figure 3, as shown in Figure 4, TEM is as Fig. 5 institute for SEM for XRD.By the Ge@MCF composite material, acetylene black and the Kynoar that obtain in mass ratio 75: 15: 10 grinding even application on Copper Foil, be made into electrode slice.In vacuum glove box, using lithium metal as reference electrode with to electrode, 1M LiClO
4eC+EMC+DMC (EC/EMC/DMC=1/1/1 v/v) be electrolyte, be assembled into battery and test, voltage range is 0.01-3 V.This lithium ion battery negative material is at 200 mA g
-1initial discharge specific capacity under current density is 1444 mAh g
-1, after charge and discharge cycles 50 times, reversible specific capacity is stabilized in 700 mAh g
-1; At big current 1 A g
-1lower circulation more than 500 times, specific capacity is still up to 389 mAh g
-1, higher than the theoretical specific capacity 372 mAh g of commercialization
-1, demonstrate high specific capacity and good stable circulation performance, concrete chemical property as Fig. 6,7, shown in 8.
Embodiment 2
1. the preparation of mesoporous carbon fiber (MCF)
Get the LN of 0.710 g, the PAN of 0.710 g and the DMF solvent of 10 ml, after stirring, obtain LN/PAN composite fibre by electrostatic spinning; The LN/PAN composite fibre obtained is placed in after distilled water etches 48 h, in the air dry oven of 70 DEG C, carries out drying; Dried fiber is placed in lower 280 DEG C of process 1 h of Muffle furnace air atmosphere, in tube furnace, is warming up to 700 DEG C and constant temperature 2 h with the heating rate of 1.5 DEG C/min under nitrogen atmosphere; Finally, be heated to 850 DEG C and adopt CO
2gas activation 1 h, obtains mesoporous carbon fiber (MCF).
2. the preparation of germanium-mesoporous carbon fiber (Ge@MCF) composite material
Get MCF and the red fuming nitric acid (RFNA) of 5 ml, the distilled water of 5 ml of 50 mg, load in polytetrafluoroethyllining lining, hydro-thermal reaction 60 min at 60 DEG C, then centrifugal, washing; The GeCl of MCF and 3 ml obtained will be washed
4, 10 ml absolute ethyl alcohol mix, magnetic agitation 20 min ultrasonic 30 min, obtain the MCF-GeCl mixed
4solution; By MCF-GeCl
4the magnetic stirring apparatus that mixed solution is placed in 18 ~ 26 DEG C is stirred to solvent volatilize completely, obtains MCF@GeCl
4composite material.
3. the preparation of lithium ion battery negative material
By MCF@GeCl obtained above
4composite material in tube furnace, N
2/ H
2be heated to 300 DEG C with the heating rate of 2.0 DEG C/min under mixed atmosphere, be then heated to 600 DEG C and constant temperature 3 h with the heating rate of 1.0 DEG C/min, obtain Ge@MCF composite material.By the Ge@MCF composite material, acetylene black and the Kynoar that obtain in mass ratio 75: 15: 10 grinding even application on Copper Foil, be made into electrode slice.In vacuum glove box, using lithium metal as reference electrode with to electrode, 1M LiClO
4eC+EMC+DMC (EC/EMC/DMC=1/1/1 v/v) be electrolyte, be assembled into battery and test, voltage range is 0.01-3 V.
Embodiment 3
1. the preparation of mesoporous carbon fiber (MCF)
Get the LN of 0.994 g, the PAN of 0.426 g and the DMF solvent of 10 ml, after stirring, obtain LN/PAN composite fibre by electrostatic spinning; The LN/PAN composite fibre obtained is placed in after distilled water etches 48 h, in the air dry oven of 70 DEG C, carries out drying; Dried fiber is placed in lower 280 DEG C of process 1 h of Muffle furnace air atmosphere, in tube furnace, is warming up to 700 DEG C and constant temperature 2 h with the heating rate of 1.5 DEG C/min under nitrogen atmosphere; Finally, be heated to 850 DEG C and adopt CO
2gas activation 1 h, obtains mesoporous carbon fiber (MCF).
2. the preparation of germanium-mesoporous carbon fiber (Ge@MCF) composite material
Get MCF and the red fuming nitric acid (RFNA) of 5 ml, the distilled water of 5 ml of 50 mg, load in polytetrafluoroethyllining lining, hydro-thermal reaction 60 min at 60 DEG C, then centrifugal, washing; The GeCl of MCF and 4.6 ml obtained will be washed
4, 10 ml absolute ethyl alcohol mix, magnetic agitation 20 min ultrasonic 30 min, obtain the MCF-GeCl mixed
4solution; By MCF-GeCl
4the magnetic stirring apparatus that mixed solution is placed in 18 ~ 26 DEG C is stirred to solvent volatilize completely, obtains MCF@GeCl
4composite material.
3. the preparation of lithium ion battery negative material
By MCF@GeCl obtained above
4composite material in tube furnace, N
2/ H
2be heated to 300 DEG C with the heating rate of 2.0 DEG C/min under mixed atmosphere, be then heated to 600 DEG C and constant temperature 3 h with the heating rate of 1.0 DEG C/min, obtain Ge@MCF composite material.By the Ge@MCF composite material, acetylene black and the Kynoar that obtain in mass ratio 75: 15: 10 grinding even application on Copper Foil, be made into electrode slice.In vacuum glove box, using lithium metal as reference electrode with to electrode, 1M LiClO
4eC+EMC+DMC (EC/EMC/DMC=1/1/1 v/v) be electrolyte, be assembled into battery and test, voltage range is 0.01-3 V.
Embodiment 4
1. the preparation of mesoporous carbon fiber (MCF)
Get the LN of 0.994 g, the PAN of 0.426 g and the DMF solvent of 10 ml, after stirring, obtain LN/PAN composite fibre by electrostatic spinning; The LN/PAN composite fibre obtained is placed in after distilled water etches 48 h, in the air dry oven of 70 DEG C, carries out drying; Dried fiber is placed in lower 280 DEG C of process 1 h of Muffle furnace air atmosphere, in tube furnace, is warming up to 700 DEG C and constant temperature 2 h with the heating rate of 5 DEG C/min under nitrogen atmosphere; Finally, be heated to 850 DEG C and adopt CO
2gas activation 1 h, obtains mesoporous carbon fiber (MCF).
2. the preparation of germanium-mesoporous carbon fiber (Ge@MCF) composite material
Get MCF and the red fuming nitric acid (RFNA) of 5 ml, the distilled water of 5 ml of 50 mg, load in polytetrafluoroethyllining lining, hydro-thermal reaction 60 min at 60 DEG C, then centrifugal, washing; The GeCl of MCF and 3 ml obtained will be washed
4, 10 ml absolute ethyl alcohol mix, magnetic agitation 20 min ultrasonic 30 min, obtain the MCF-GeCl mixed
4solution; By MCF-GeCl
4the magnetic stirring apparatus that mixed solution is placed in 18 ~ 26 DEG C is stirred to solvent volatilize completely, obtains MCF@GeCl
4composite material.
3. the preparation of lithium ion battery negative material
By MCF@GeCl obtained above
4composite material in tube furnace, N
2/ H
2be heated to 300 DEG C with the heating rate of 2.0 DEG C/min under mixed atmosphere, be then heated to 600 DEG C and constant temperature 3 h with the heating rate of 1.0 DEG C/min, obtain Ge@MCF composite material.By the Ge@MCF composite material, acetylene black and the Kynoar that obtain in mass ratio 75: 15: 10 grinding even application on Copper Foil, be made into electrode slice.In vacuum glove box, using lithium metal as reference electrode with to electrode, 1M LiClO
4eC+EMC+DMC (EC/EMC/DMC=1/1/1 v/v) be electrolyte, be assembled into battery and test, voltage range is 0.01-3 V.
Claims (9)
1. a germanium
-the preparation method of mesoporous carbon fiber composite lithium cell cathode material, is characterized in that, comprise following steps:
(1) preparation of mesoporous carbon fiber: sodium lignin sulfonate is mixed with polyacrylonitrile, then add dimethyl formamide and be made into spinning solution, obtain LN/PAN composite fibre by electrostatic spinning; The LN/PAN composite fibre obtained is placed in solvent, after etching 12 ~ 48 h, the dry fiber obtaining loose structure in the air dry oven of 70 DEG C; By the fiber of this loose structure in Muffle furnace, 200 ~ 300 DEG C of pre-oxidation 1 ~ 3 h under air atmosphere, in tube furnace under nitrogen atmosphere, adopt progressively temperature-raising method to calcine the fiber after pre-oxidation treatment, calcining heat 500 ~ 800 DEG C, calcination time 1 ~ 3 h; Finally, be heated to 850 DEG C and adopt CO
2gas activation 1 h, can obtain the carbon fiber of special meso-hole structure;
(2) preparation of germanium-mesoporous carbon fiber (Ge@MCF) composite material: get ratio of quality and the number of copies for (3 ~ 8): MCF and GeCl of (2 ~ 7)
4hydro-thermal reaction is carried out in mixing, after the product drying of acquisition, in tube furnace, is heated to 400 ~ 700 DEG C under inert atmosphere with the heating rate of 1.0 ~ 10 DEG C/min, obtains germanium-mesoporous carbon fibrous composite;
(3) preparation of lithium ion battery negative material: the Ge@MCF composite material of above-mentioned preparation and acetylene black, Kynoar 75 ~ 80: 10 ~ 15: 5 ~ 10 are prepared burden in mass ratio, be coated in equably on copper sheet after grinding, and dry, obtain lithium ion battery negative material.
2. a kind of germanium according to claim 1
-the preparation method of mesoporous carbon fiber composite lithium cell cathode material, is characterized in that: in described step (1), the concentration of spinning solution is 8 ~ 15%.
3. a kind of germanium according to claim 1
-the preparation method of mesoporous carbon fiber composite lithium cell cathode material, is characterized in that: the portion rate (1 ~ 9) of LN and PAN in described step (1): (1 ~ 9).
4. a kind of germanium according to claim 1
-the preparation method of mesoporous carbon fiber composite lithium cell cathode material, is characterized in that: the electrospinning conditions in described step (1) is: voltage 15 ~ 25 kv, receiving range 13 ~ 18 cm, spinning solution plug-flow speed 0.1 ~ 1 ml/h, electrospinning temperature 25 ~ 45 DEG C.
5. a kind of germanium according to claim 1
-the preparation method of mesoporous carbon fiber composite lithium cell cathode material, is characterized in that: in described step (1), the etching solution of LN/PAN composite fibre is distilled water or aqueous slkali water solvent.
6. a kind of germanium according to claim 1
-the preparation method of mesoporous carbon fiber composite lithium cell cathode material, is characterized in that: the progressively temperature-raising method in described step (1) refers to that heating rate is 1 ~ 5 DEG C/min.
7. a kind of germanium according to claim 1
-the preparation method of mesoporous carbon fiber composite lithium cell cathode material, it is characterized in that: the hydro-thermal reaction in described step (2) refer to mass ratio be 80 ~ 85: 10 ~ 12: 5 ~ 8 MCF and red fuming nitric acid (RFNA), distilled water put into reactor, at 50 ~ 80 DEG C after water-bath 0.5 ~ 1 h with GeCl
4mixing, magnetic agitation 20 min ultrasonic process 30 min.
8. a kind of germanium according to claim 1
-the preparation method of mesoporous carbon fiber composite lithium cell cathode material, it is characterized in that: the drying that hydro-thermal reaction in described step (2) obtains product refer to product is placed in 10 ~ 30 DEG C magnetic stirring apparatus on be stirred to solvent and volatilize completely, and in the drying box of 50 ~ 100 DEG C dry 2 ~ 8 h.
9. a kind of germanium according to claim 1
-the preparation method of mesoporous carbon fiber composite lithium cell cathode material, is characterized in that: the inert atmosphere in described step (2) refers to N
2/ H
2gaseous mixture.
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| CN112397724A (en) * | 2020-11-16 | 2021-02-23 | 珠海冠宇动力电池有限公司 | Lithium ion battery positive plate and preparation method thereof and lithium ion battery |
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| CN108011086B (en) * | 2017-11-22 | 2020-06-02 | 商丘师范学院 | Preparation method of Ge/C composite nanofiber |
| CN109183197A (en) * | 2018-08-27 | 2019-01-11 | 江苏吉庆管材有限公司 | A kind of antidetonation anticorrosion carbon fiber pipeline and preparation method thereof |
| CN109244490A (en) * | 2018-09-12 | 2019-01-18 | 江苏师范大学 | A kind of preparation method of cementite@nitrogen-doped carbon nanocatalyst |
| CN110065964A (en) * | 2019-05-30 | 2019-07-30 | 南京欣益浩信息科技有限公司 | A kind of carbon fiber helps method growth to have nano pore organo-mineral complexing germania nanoparticles line method |
| CN112397724A (en) * | 2020-11-16 | 2021-02-23 | 珠海冠宇动力电池有限公司 | Lithium ion battery positive plate and preparation method thereof and lithium ion battery |
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