CN106099106A - Ultrafast fill lithium ion battery negative material, its preparation method and lithium ion battery - Google Patents

Ultrafast fill lithium ion battery negative material, its preparation method and lithium ion battery Download PDF

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CN106099106A
CN106099106A CN201610705609.8A CN201610705609A CN106099106A CN 106099106 A CN106099106 A CN 106099106A CN 201610705609 A CN201610705609 A CN 201610705609A CN 106099106 A CN106099106 A CN 106099106A
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lithium ion
ion battery
negative material
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battery negative
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CN106099106B (en
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王琳琳
徐美兰
徐菁利
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Shanghai University of Engineering Science
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1393Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00Batteries for particular applications
    • H01M2220/30Batteries in portable systems, e.g. mobile phone, laptop
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • General Chemical & Material Sciences (AREA)
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Abstract

The present invention relates to a kind of ultrafast lithium ion battery negative material, its preparation method and lithium ion battery of filling, concrete preparation method is, uses metal-oxide MxNyOz(M, N=Zn, Cu, Fe, Mn, Ge, Co, Ni, Ti, V, Cr, Cd, Sn etc., 0≤x≤3;0≤y≤3;1≤z≤5) nanometer rods is template, with itrogenous organic substance in-situ polymerization, presoma is obtained after carbonization, presoma is added stripper plate reagent, the meso-porous hollow bar-shaped carbon Nano capsule negative material of N doping is obtained after process, compared with doing lithium ion battery with existing material with carbon element, under lasting high current density, ultrafast discharge and recharge can be realized simultaneously and capacity is high, cycle life overlength.After 10A/g electric current density discharge and recharge, circulation 10,000 circle, capacity is stably held in 370mA h/g;After 30A/g excess current densities discharge and recharge, circulation 10,000 circle, capacity is still stably held in 290mA h/g, has fabulous cyclical stability and high power capacity, and preparation method is simple, it is not necessary to complex device, can be prepared on a large scale, be suitable to commercial production.

Description

Ultrafast fill lithium ion battery negative material, its preparation method and lithium ion battery
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of ultrafast fill lithium ion battery negative material, its Preparation method and lithium ion battery.
Background technology
Developing rapidly of portable communication apparatus, urgent needs high power density, high capacity density, have extended cycle life, can The lithium ion battery of ultrafast discharge and recharge.Material with carbon element enrich, low cost, can avoid when doing lithium ion battery negative because of use silicon, stannum, Metal-oxides etc. do the enormousness expansion issues that negative material causes, and are especially suitable for as lithium ion battery negative material. But, the most business-like lithium ion battery with graphite as negative material, its theoretical specific capacity is on the low side (372mAh/g), restriction The raising of lithium ion battery capacity, it is impossible to meet following high power capacity, the demand of long-life electron equipment, current alternative graphite New Type of Carbon negative material obtain the research of increasing scholar.The carbon of N doping, as negative material, can reach high filling Discharge-rate, but under lasting high current density discharge and recharge, there is the problem that capacity is on the low side, cycle life is short, it is impossible to meet High power density, high capacity density, have extended cycle life and can super-quick charging electric discharge demand.
Summary of the invention
The purpose of the present invention be contemplated to solve the problems referred to above and provide a kind of ultrafast fill, high power capacity, extra long life performance Lithium ion battery negative material, its preparation method and lithium ion battery.
The purpose of the present invention is achieved through the following technical solutions:
A kind of ultrafast fill, the preparation method of the lithium ion battery negative material of high power capacity, extra long life performance, specifically include Following steps:
(1) use metal oxide nanorods as template, metal oxide nanorods is distributed in solution;
(2) in the solution of step (1), add itrogenous organic substance and buffer, itrogenous organic substance is received with metal-oxide Rice rod carries out in-situ polymerization;
(3) after the solids in step (2) mixed solution being centrifuged, cleaning, dry, carbon in nitrogen or ar gas environment Change, obtain presoma;
(4) presoma step (3) obtained adds stripper plate reagent, is centrifuged, cleans, dries, i.e. obtain lithium after process Ion battery cathode material.
The molecular formula of the metal oxide nanorods described in step (1) is MxNyOz, wherein M, N=Zn, Cu, Fe, Mn, Ge, Co, Ni, Ti, V, Cr, Cd or Sn, 0≤x≤3;0≤y≤3;1≤z≤5.
Preferably, described metal oxide nanorods be selected from zinc oxide, ferrum oxide, manganese oxide, germanium oxide, copper germanate, Zinc or the one of zinc germanate.
Preferably, a length of 200-2000nm of the metal oxide nanorods described in step (1), external diameter is 10- 500nm, described solution is ethanol water, and more than metal oxide nanorods, the mass ratio of ethanol water is 1:200-250.
Preferably, the itrogenous organic substance described in step (2) is selected from dopamine, dopamine hydrochloride, polyurethane, pyrroles, hydramine Or the one of nitrate, described buffer is trishydroxymethylaminomethane, described metal oxide nanorods and nitrogenous have The mass ratio of machine thing is 1:0.2-5, and metal oxide nanorods is 2-5:1 with the mass ratio of buffer.
Preferably, the temperature of the in-situ polymerization described in step (2) is 20-25 DEG C, and the time is 10-30h.
Preferably, the temperature of the carbonization described in step (3) is 400-900 DEG C, and the time is 4-12h.
Preferably, the one in hydrochloric acid, sulphuric acid, nitric acid, acetic acid or carbonic acid of the stripper plate reagent described in step (4) or Multiple mixture, the time of stripper plate agent treated is 1h-7 days, more preferably 1-3 days, most preferably 2.5 days.
A kind of lithium ion battery negative material, described lithium ion battery negative material uses above-mentioned preparation method system ?.
A kind of lithium ion battery, including positive pole, negative pole, barrier film and electrolyte, described negative pole uses above-mentioned lithium ion Cell negative electrode material prepares.
Preparing lithium ion battery uses usual technological means to prepare, and concretely comprises the following steps:
(1) lithium ion battery negative material, binding agent and conductive agent are mixed, add dispersant furnishing slurry, coating On Copper Foil, after vacuum dried, roll-in, prepare into negative plate;
(2) prepared negative plate is assembled with positive pole lithium sheet, barrier film and electrolyte, i.e. prepare lithium ion battery.
Above-mentioned binding agent is polyvinyladine floride (PVDF), and conductive agent is Super-P, and dispersant is N-Methyl pyrrolidone (NMP), lithium ion battery negative material and binding agent polyvinyladine floride (PVDF), conductive agent Super-P are according to the weight of 8:1:1 Than mixing;
Above-mentioned positive pole uses lithium sheet;Barrier film uses microporous polypropylene membrane;Electrolyte uses ethylene carbonate (EC), carbonic acid Dimethyl ester (DMC) and the mixed liquor of Ethyl methyl carbonate (EMC), use the LiPF of 1mol/L6Three component mixed solvents, wherein The mass ratio of EC, DMC and EMC is 1:1:1.
Compared with prior art, the present invention uses metal oxide nanorods as template, and nanometer rods can be adjusted flexibly Size, obtains the electrode material that series length is different with external diameter, finally prepares the meso-porous hollow bar-shaped carbon Nano capsule of N doping Negative material.Using in the nitrogen component that the method produces, pyrroles's nitrogen (N-5) and pyridine nitrogen (N-6) content ratio are high, by introducing Super a high proportion of N-5 and N-6, creates substantial amounts of edge and surface " cavity " defect sites, adds the specific capacity of material, again Create loose structure, further enhancing the chemical property of material;The N-Q of the low low content of graphite nitrogen (N-Q) content ratio Be conducive to maintaining the stability of structure, the negative material additionally prepared to have the bar-shaped capsule structure of closing meso-porous hollow of uniqueness, tool There is good mechanical stability, N-5 and the N-6 doping of high-load and the synergism of mesoporous space bar-shaped capsule unique texture, The volumetric expansion in charge and discharge process of this negative material be can effectively suppress, electron conduction and specific capacity improved, and the biggest Under electric current density, it is achieved ultrafast discharge and recharge and capacity are high, have extended cycle life.
Use the lithium ion battery that lithium ion battery negative material of the present invention prepares, charge and discharge under 10A/g high current density Electricity, after circulation 10000 circle, capacity is stably held in about 370, discharge and recharge under 30A/g excess current densities, circulation 10000 circle Rear capacity is stably held in about 290, has fabulous cyclical stability and high power capacity.Additionally, preparation method of the present invention is simple, Need not complex device, can be prepared on a large scale, be suitable to commercial production.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing In having technology to describe, the required accompanying drawing used is briefly described, and certainly, the accompanying drawing in below describing is only the present invention's Embodiment, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to according to provide Accompanying drawing obtains other accompanying drawing.
Fig. 1 is the TEM figure of negative material of the present invention;
Fig. 2 is the graceful spectrogram of negative material of the present invention;
Fig. 3 is the N1s XPS figure of negative material of the present invention;
Fig. 4 is lithium ion battery charge and discharge cycles curve when electric current density is 10A/g;
Fig. 5 is lithium ion battery charge and discharge cycles curve when electric current density is 30A/g.
Detailed description of the invention
In order to further illustrate the present invention, the one that provides the present invention below in conjunction with embodiment is ultrafast fills, high power capacity, super Long-life performance lithium ion battery negative material, its preparation method and lithium ion battery are described in detail, but can not be managed Solve as limiting the scope of the present invention.
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Being 480nm by average length, external diameter is the zinc germanate nanometer rods template of 65nm, weighs 0.15g, is distributed to 20ml second In the mixed solution of alcohol and 15ml water, and weigh dopamine hydrochloride 0.23g, add in above-mentioned solution, be subsequently adding 0.05g tri- (methylol) aminomethane and 10ml water, after being stirred at room temperature 20h.After being centrifuged, cleaning, dry, pipe put into by the sample after drying In formula stove, first it is passed through argon and gets rid of air, be continually fed into argon, be then warmed up to 550 DEG C, carbonization 4h, finally cool down with stove Sample to room temperature, obtain presoma.Then weigh 0.2g presoma to be soaked in 80mL chloroazotic acid, after standing 1 day, centrifugal, clear Wash, dry, obtain lithium ion battery negative material.
Anticathode material carries out transmission electron microscope detection, as it is shown in figure 1, as seen from Figure 1, negative material is hollow to result Bar-shaped capsule structure, average length is 500nm, and mean outside diameter is 80nm;Fig. 2 is the Raman spectrogram of negative material, can by Fig. 2 To find out ID/IG=2.04, show that material with carbon element has a lot of defect, these " cavity " defect sites, add the specific volume of material Amount, enhances the chemical property of material, and Fig. 3 is the XPS figure of the N1S of negative material, and as seen from Figure 3, the present embodiment is born In the material of pole, the nitrogen of doping exists with pyrroles's nitrogen (N-5), pyridine nitrogen (N-6), three kinds of forms of graphite nitrogen (N-Q), and wherein three contains Amount percentage ratio is: 34:43:23.
The lithium ion battery negative material that the present embodiment is obtained and binding agent polyvinyladine floride (PVDF), conductive agent Super-P mixes according to the weight ratio of 8:1:1, adds appropriate N-Methyl pyrrolidone (NMP) as dispersant furnishing slurry, painting Overlay on Copper Foil, and vacuum dried, roll-in, it is prepared as negative plate.Positive pole uses lithium sheet, and barrier film uses microporous polypropylene membrane, Use the mixed liquor of ethylene carbonate (EC), dimethyl carbonate (DMC) and Ethyl methyl carbonate (EMC) as electrolyte, mass ratio For 1:1:1, use the LiPF of 1mol/L6Three component mixed solvents as electrolyte, microporous polypropylene membrane is barrier film, by negative pole Sheet, positive plate, barrier film and electrolyte are assembled into CR2016 simulated battery.
The electric current using 10A/g, 30A/g carries out constant current charge-discharge experiment, and (wherein the electric current density of first lap is 400mA/ G), the cycle performance of the lithium ion battery that test prepares, charging/discharging voltage is limited in 0.01-3V, uses Shenzhen's new Weir electricity The chemical property of the Neware CT-3008 battery test system test battery of sub-company limited, tests at room temperature condition, Fig. 4 For being charge and discharge cycles curve during 10A/g, as shown in Figure 4, discharge and recharge under 10A/g high current density in electric current density, follow Ring 10, after 000 circle, capacity is stably held in 370, has good cyclical stability and high power capacity.Fig. 5 is in electric current density to be Charge and discharge cycles curve during 30A/g, as shown in Figure 5, discharge and recharge under 30A/g excess current densities, after circulation 10,000 circle Capacity is stably held in 290, has fabulous cyclical stability and high power capacity.
Embodiment 2
It is 480nm by average length, the zinc germanate nanometer rods template of a diameter of 65nm, weigh weight 0.15g, be distributed to In the mixed solution of 20mL ethanol and 15mL water, and weigh dopamine hydrochloride 0.075g, add in above-mentioned solution, be subsequently adding 0.05g tri-(methylol) aminomethane, and 10mL water, after after 20h is stirred at room temperature, being centrifuged, cleaning, dry, the sample after drying Product are put in tube furnace, are first passed through argon and get rid of air, are continually fed into argon, are then warmed up to 550 DEG C, carbonization 4h.Finally with Stove samples after being cooled to room temperature, obtains presoma;Then weigh 0.2g presoma to be soaked in 80mL chloroazotic acid, after standing 1 day, Centrifugal, cleaning, drying, obtain negative material.
By the lithium ion battery negative material that obtains with the inclined fluorine ethylene of binding agent (PVDF), conductive agent Super-P according to 8: The weight ratio mixing of 1:1, adds appropriate N-Methyl pyrrolidone (NMP) as dispersant furnishing slurry, is coated on Copper Foil, and Vacuum dried, roll-in, is prepared as negative plate;Positive pole uses lithium sheet, uses the LiPF of 1mol/L6Three component mixed solvent EC : DMC: EMC=1:1:1 liquid is electrolyte, and microporous polypropylene membrane is barrier film, is assembled into CR2016 simulated battery, and gained battery exists Discharge and recharge under the high current density of 10A/g, after circulation 10000 circle, capacity is stably held in about 320;Big electric current at 30A/g Discharge and recharge under density, after circulation 10,000 circle, capacity is stably held in 250mA about h/g.
Embodiment 3
It is 900nm by average length, the copper germanate nanometer rods template of a diameter of 40nm, weigh weight 0.15g, be distributed to In the mixed solution of 20mL ethanol and 15mL water, and weigh dopamine hydrochloride 0.23g, add in above-mentioned solution, be subsequently adding 0.05g tri-(methylol) aminomethane, and 10mL water, after 20h is stirred at room temperature, centrifugal, clean, the sample after drying, after drying Product are put in tube furnace, are first passed through argon and get rid of air, are continually fed into argon, are then warmed up to 550 DEG C, carbonization 4h.Finally with Stove samples after being cooled to room temperature, obtains presoma;Then weigh 0.2g presoma to be soaked in 80mL chloroazotic acid, after standing 1 day, Centrifugal, cleaning, drying, obtain negative material.
The lithium ion battery negative material that the present embodiment is obtained and the inclined fluorine ethylene of binding agent (PVDF), conductive agent Super- P mixes according to the weight ratio of 8:1:1, adds appropriate N-Methyl pyrrolidone (NMP) as dispersant furnishing slurry, is coated in copper On paper tinsel and vacuum dried, roll-in, is prepared as negative plate;Positive pole uses lithium sheet, uses the LiPF of 1mol/L6Three components mix Bonding solvent EC: DMC: EMC=1:1:1 liquid is electrolyte, and microporous polypropylene membrane is barrier film, is assembled into CR2016 simulated battery.Institute Obtaining battery discharge and recharge under 10A/g high current density, after circulation 10,000 circle, capacity is stably held in 300mA about h/g, Discharge and recharge under 30A/g high current density, after circulation 10,000 circle, capacity is stably held in 210mA about h/g.
Embodiment 4
A kind of lithium ion battery negative material, uses following methods to prepare:
(1) using zinc oxide nano rod as template, a length of 200nm of zinc oxide nano rod, external diameter is 10nm, by 1g Zinc oxide nano rod is distributed in 200g ethanol water;
(2) dopamine and the 0.2g trishydroxymethylaminomethane of 0.1g are added in the solution, by dopamine and zinc oxide nano Rice rod carries out in-situ polymerization, stirs 10h under room temperature;
(3) after the solids in step (2) mixed solution being centrifuged, cleaning, dry, carbonization in ar gas environment, obtain Presoma, the temperature of carbonization is 400 DEG C, and the time is 12h;
(4) presoma step (3) obtained adds process 1h in sulphuric acid, is centrifuged, cleans, dries, i.e. obtain after process Lithium ion battery negative material.
Embodiment 5
A kind of lithium ion battery negative material, uses following methods to prepare:
(1) using zinc germanate nanometer rods is 200nm as template, a length of 1000nm of zinc germanate nanometer rods, external diameter, will 1g zinc germanate nanometer rods is distributed in 230g ethanol water;
(2) polyurethane and the 0.4g trishydroxymethylaminomethane of 5g are added in the solution, by polyurethane and zinc germanate nanometer Rod carries out in-situ polymerization, stirs 20h under room temperature;
(3) after the solids in step (2) mixed solution being centrifuged, cleaning, dry, carbonization in ar gas environment, obtain Presoma, the temperature of carbonization is 600 DEG C, and the time is 8h;
(4) presoma step (3) obtained adds process 2.5 days in hydrochloric acid, is centrifuged, cleans, dries, to obtain final product after process To lithium ion battery negative material.
Embodiment 6
A kind of lithium ion battery negative material, uses following methods to prepare:
(1) using ferric oxide nano rod is 500nm as template, a length of 2000nm of ferric oxide nano rod, external diameter, will 1g ferric oxide nano rod is distributed in 250g ethanol water;
(2) add pyrroles and the 0.5g trishydroxymethylaminomethane of 10g in the solution, pyrroles is entered with ferric oxide nano rod Row in-situ polymerization, stirs 30h under room temperature;
(3) after the solids in step (2) mixed solution being centrifuged, cleaning, dry, carbonization in nitrogen environment, obtain Presoma, the temperature of carbonization is 900 DEG C, and the time is 4h;
(4) presoma step (3) obtained adds process 7 days in nitric acid, is centrifuged, cleans, dries, i.e. obtain after process Lithium ion battery negative material.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For Yuan, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (10)

1. the ultrafast preparation method filling lithium ion battery negative material, it is characterised in that specifically include following steps:
(1) use metal oxide nanorods as template, metal oxide nanorods is distributed in solution;
(2) in the solution of step (1), itrogenous organic substance and buffer are added, by itrogenous organic substance and metal oxide nanorods Carry out in-situ polymerization;
(3) after the solids in step (2) mixed solution being centrifuged, cleaning, dry, carbonization in nitrogen or ar gas environment, To presoma;
(4) presoma step (3) obtained adds stripper plate reagent, is centrifuged, cleans, dries, i.e. obtain lithium ion after process Cell negative electrode material.
The preparation method of a kind of lithium ion battery negative material the most according to claim 1, it is characterised in that step (1) The molecular formula of described metal oxide nanorods is MxNyOz, wherein M, N=Zn, Cu, Fe, Mn, Ge, Co, Ni, Ti, V, Cr, Cd or Sn, 0≤x≤3;0≤y≤3;1≤z≤5.
The preparation method of a kind of lithium ion battery negative material the most according to claim 2, it is characterised in that described gold Belong to oxide nano-rod selected from zinc oxide, ferrum oxide, manganese oxide, germanium oxide, copper germanate, zinc or the one of zinc germanate.
The preparation method of a kind of lithium ion battery negative material the most according to claim 1, it is characterised in that step (1) The a length of 200-2000nm of described metal oxide nanorods, external diameter is 10-500nm, and described solution is that ethanol is water-soluble Liquid, metal oxide nanorods is 1:200-250 with the mass ratio of ethanol water.
The preparation method of a kind of lithium ion battery negative material the most according to claim 1, it is characterised in that step (2) Described itrogenous organic substance is selected from dopamine, dopamine hydrochloride, polyurethane, pyrroles, hydramine or the one of nitrate, and described is slow Rushing liquid is trishydroxymethylaminomethane, and metal oxide nanorods is 1:0.2-5 with the mass ratio of itrogenous organic substance, burning Thing nanometer rods is 2-5:1 with the mass ratio of buffer.
The preparation method of a kind of lithium ion battery negative material the most according to claim 1, it is characterised in that step (2) The temperature of described in-situ polymerization is 20-25 DEG C, and the time is 10-30h.
The preparation method of a kind of lithium ion battery negative material the most according to claim 1, it is characterised in that step (3) The temperature of described carbonization is 400-900 DEG C, and the time is 4-12h.
The preparation method of a kind of lithium ion battery negative material the most according to claim 1, it is characterised in that step (4) Described stripper plate reagent one or more mixture in hydrochloric acid, sulphuric acid, nitric acid, acetic acid or carbonic acid, stripper plate reagent The time processed is 1h-7 days.
9. one kind ultrafast is filled lithium ion battery negative material, it is characterised in that described lithium ion battery negative material uses power Profit requires that the preparation method described in 1-8 any one prepares.
10. a lithium ion battery, including positive pole, negative pole, barrier film and electrolyte, it is characterised in that described negative pole uses power Profit requires that the lithium ion battery negative material described in 9 prepares.
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CN108011105A (en) * 2017-11-28 2018-05-08 中南大学 Carbon nanosheet material, preparation thereof and application thereof in sodium-ion battery
CN109647584A (en) * 2018-12-10 2019-04-19 桂林理工大学 A kind of sand milling method of modifying of lithium ion battery mineral negative electrode material
CN109817948A (en) * 2019-03-04 2019-05-28 河南师范大学 A kind of preparation method of lithium ion battery carbon coating MnO/ crystalline flake graphite combination electrode material
CN111874940A (en) * 2020-07-13 2020-11-03 滁州学院 Preparation method and application of tubular tin dioxide and carbon-coated tubular tin dioxide nanocomposite
CN113381015A (en) * 2021-06-18 2021-09-10 郑州大学 Nitrogen-doped hollow amorphous carbon shell material, preparation method and application
CN114538500A (en) * 2022-03-09 2022-05-27 郑州轻工业大学 Bar-shaped structure Zn2GeO4Material, preparation method and application thereof
WO2023115503A1 (en) * 2021-12-20 2023-06-29 超威电源集团有限公司 Preparation method for iron-cobalt phosphide/carbon composite material having layered structure, and button cell

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