CN105552354B - A kind of preparation method of lithium ion battery negative material - Google Patents

A kind of preparation method of lithium ion battery negative material Download PDF

Info

Publication number
CN105552354B
CN105552354B CN201610151315.5A CN201610151315A CN105552354B CN 105552354 B CN105552354 B CN 105552354B CN 201610151315 A CN201610151315 A CN 201610151315A CN 105552354 B CN105552354 B CN 105552354B
Authority
CN
China
Prior art keywords
nano
particle
sio
water
hours
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201610151315.5A
Other languages
Chinese (zh)
Other versions
CN105552354A (en
Inventor
刘伟良
杨婷婷
赵丹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qilu University of Technology
Original Assignee
Qilu University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qilu University of Technology filed Critical Qilu University of Technology
Priority to CN201610151315.5A priority Critical patent/CN105552354B/en
Publication of CN105552354A publication Critical patent/CN105552354A/en
Application granted granted Critical
Publication of CN105552354B publication Critical patent/CN105552354B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • 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
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 discloses a kind of preparation method of lithium ion battery negative material, the negative material is the complex microsphere of special yolk structure, and the stratum nucleare of the complex microsphere is ferroso-ferric oxide（Fe3O4）, shell is the cavity between stratum nucleare and shell to be formed after etching containing mesoporous C, N layer.Preparation method is：First, sol-gal process synthetic silica（SiO2）Nano-particle, hydro-thermal method synthesize Fe3O4Nano-particle；Then, in Fe3O4One layer of SiO of outer cladding2, then in SiO2One layer of outer cladding of layer is by SiO2The composite shell of nano-particle and melamine resin composition；Finally, by calcining and etching obtains yolk structure composite microballoon.Material structure of the present invention is novel, and cavity can inhibit Fe3O4The bulk effect of particle, the mesoporous diffusion velocity that can accelerate lithium ion improve electrochemical reaction speed, moreover it is possible to improve multiplying power and cycle performance while improving material electric conductivity and specific capacity.

Description

A kind of preparation method of lithium ion battery negative material
Technical field
The invention belongs to energy technology fields and technical field of lithium ion, and in particular to a kind of negative electrode of lithium ion battery The preparation method of material.
Background technology
In recent years, for graphite because of its charge-discharge performance stabilization, theoretical specific capacity is 372 mAh g−1, it has been widely used In the research of lithium ion battery negative material, but with the development of science and technology and electronic product, existing electric energy storage device is difficult In meeting the new market demand.Data show, nano level transition metal oxide（MxOy, M=Mn, Fe, Co, Ni etc.）Theoretical ratio Capacity is higher, big as new energy materials development space.Wherein Fe3O4Theoretical capacity is 924mAh g−1, stability is good, price Cheaply, it derives from a wealth of sources, is gradually used as lithium ion battery negative material.But Fe3O4Conductivity itself is low, easily occurs when cycle solidifying Phenomena such as poly- and bulk effect, need to be further modified as negative material could meet real needs.
The Mn oxide lithium ion battery negative material of N doping C claddings has been made in Wang Jian-Gan et al., illustrates that N mixes Miscellaneous carbon material has higher electronic transmission performance.Patent of invention CN104779378A describes a kind of mesoporous carbon fiber of germanium- The preparation method of composite lithium ion battery negative material utilizes water-soluble quarter to solve the problems, such as volume expansion of germanium during removal lithium embedded Erosion method prepares matrix of the carbon fiber as lithium cell cathode material of special meso-hole structure, and is compounded to form Ge MCF with ge source Composite material has effectively buffered volume expansion of germanium during removal lithium embedded, while having improved the specific volume of lithium cell cathode material Amount and cycle performance.Imagination space is provided for the novel lithium cell cathode material of design structure.
For lithium ion battery negative material structural instability in the prior art, the shortcomings that poor circulation, the present invention carries A kind of Fe with special construction is gone out3O4The preparation method of composite material.Fe with special construction prepared by the present invention3O4 Composite material, stratum nucleare Fe3O4Material, shell are to contain mesoporous C, N layer.Stratum nucleare have higher theoretical capacity, shell it is mesoporous With high specific surface area and uniform mesopore orbit, the transmission for lithium ion provides channel.The present invention is directed to be lithium battery The research of negative material provides new approaches.
Invention content
For the above fact, a kind of preparation method of lithium ion battery negative material provided by the invention, including following step Suddenly：
（1）Six water of ferric trichloride, anhydrous sodium acetate and sodium citrate are uniformly mixed with a certain amount of ethylene glycol, are added Into autoclave, reacted 10~12 hours at 180~200 DEG C, by magnet will precipitation detach, successively use absolute ethyl alcohol and Water washing, it is dry, obtain Fe3O4Nano-particle；
（2）Absolute ethyl alcohol and ammonium hydroxide are uniformly mixed, ethyl orthosilicate is added dropwise in 20 ~ 30 minutes again under mechanical agitation To in above-mentioned mixed solution, being reacted at 20 ~ 30 DEG C 10 ~ 12 hours, absolute ethyl alcohol and water washing are used successively, it is dry, obtain SiO2 Nano-particle；
（3）By step（1）Gained Fe3O4Nano-particle, absolute ethyl alcohol and ammonium hydroxide are uniformly mixed, and at 20~25 DEG C, machinery stirs It mixes 30~a certain amount of ethyl orthosilicate is added dropwise after sixty minutes, mechanical agitation 10~12 hours is detached precipitation by magnet, according to It is secondary that absolute ethyl alcohol and water washing, drying is used to obtain Fe3O4@SiO2Nano-particle；
（4）Melamine is dissolved in 37% formalin under 50~60 DEG C of water-baths, obtains the mixed solution of homogeneous transparent；
（5）By step（2）Gained SiO2After mixing, step is added in nano-particle and water（4）Middle gained mixed solution And catalyst, it is reacted 0.5 ~ 3 hour under 50~60 DEG C of water-baths.Afterwards by step（3）Gained Fe3O4@SiO2On nano-particle is added It states in mixed solution, continues to react 2~4 hours under these conditions, precipitation is detached by magnet, is washed with water, it is dry, it obtains To Fe3O4@SiO2@（SiO2With melamine resin composite layer）Nano-particle；
（6）By step（5）Middle obtained solid product is sintered 4~6 hours in 600~850 DEG C of inert gas shielding atmosphere, Obtain Fe3O4@SiO2@（SiO2With C-N composite layers）；
（7）By step（6）Middle gained Fe3O4@SiO2@（SiO2With C-N composite layers）Nano-particle solid product, etching agent It is mixed with water, is reacted 4~8 hours at 60~85 DEG C, precipitation is detached by magnet, is washed with water, it is dry, it obtains Fe3O4@cavitys@（The mesoporous layer of C-N nano-particles）Nano-particle.
Upper step（4）Described in the molar ratio of melamine and 37% formalin be 1:1~5.
Upper step（5）Described in catalyst be formic acid, glacial acetic acid or sodium hydroxide in one kind.
Upper step（7）Described in etching agent be one kind in hydrofluoric acid or sodium hydroxide.
It is compared with the prior art, a kind of preparation method of lithium ion battery negative material provided by the invention has following excellent Point：
（1）The present invention makes full use of the magnetic responsiveness of magnetic material to detach, easy to operate simple；
（2）Fe prepared by the present invention3O4@cavitys@（The mesoporous layer of C-N nano-particles）Nano particle structure is unique, cavity energy Inhibit Fe3O4The bulk effect of particle, the mesoporous diffusion velocity that can accelerate lithium ion improve electrochemical reaction speed；
（3）Fe prepared by the present invention3O4@cavitys@（The mesoporous layer of C-N nano-particles）Nano-particle, shell C, N content are high, It is used as lithium ion battery negative material, excellent electrical property.
Specific implementation mode
The above of the present invention is further illustrated but should not be interpreted as this below by way of specific embodiment Present disclosure is only limitted to following examples.
Embodiment 1：
（1）Six water of 2.1g ferric trichlorides, 2.4g anhydrous sodium acetates and 0.35g sodium citrates are dissolved in 40ml ethylene glycol In, ultrasonic disperse forms uniform suspension in 1 hour.By the suspension under room temperature mechanical agitation 1 hour, be added to later It is reacted 10 hours in 180 DEG C in the reaction kettle of 100ml.Precipitation is detached by magnet, uses absolute ethyl alcohol and distilled water each successively It is 8 hours dry at washing 3 times, 40 DEG C, obtain Fe3O4Nano-particle；
（2）150ml absolute ethyl alcohols and 10ml ammonium hydroxide are uniformly mixed, then 5ml ethyl orthosilicates were dripped in 25 minutes Finish, is reacted at 25 DEG C 10 hours, it is 10 hours dry at using absolute ethyl alcohol and distilled water respectively to wash 3 times, 40 DEG C successively, obtain SiO2 Nano-particle；
（3）By step（1）Gained Fe3O40.15g, 100ml absolute ethyl alcohol and 6ml ammonium hydroxide are mixed evenly, 25 DEG C of water-baths After forty minutes, 4ml ethyl orthosilicates are slowly added dropwise in lower mechanical agitation, continue mechanical agitation 10 hours, and solution slowly becomes white. Precipitation is detached by magnet, it is 10 hours dry at using absolute ethyl alcohol and distilled water respectively to wash 3 times, 40 DEG C successively, obtain Fe3O4@ SiO2Nano-particle；
（4）Take 37% formalin of 1.2g melamines and 3ml, magnetic agitation 30 minutes is complete to melamine at 60 DEG C Dissolving, obtains the mixed solution of homogeneous transparent；
（5）Take step（2）Gained SiO2After mixing, step is added in nano-particle 0.1g and 100ml distilled water（4）Institute Obtain the formalin and 1.5mL glacial acetic acids dissolved with melamine, mechanic whirl-nett reaction 1 hour under 50 DEG C of water-baths.Again by step （3）Gained Fe3O4@SiO2Nano-particle 0.2g is added in above-mentioned mixed solution, and the reaction was continued under the same terms 2 hours.Pass through magnetic Iron detaches precipitation, is washed with distilled water to drying 10 hours at lacking 3 times, 60 DEG C, obtains Fe3O4@SiO2@（SiO2With melamine tree Fat composite layer）Nano-particle；
（6）By step（5）Gained nano-particle mortar grinder is placed at powder in crucible, is trained using tube furnace It burns, condition is：Ar atmosphere is enclosed, 600 DEG C, keeps the temperature 4 hours, and heating rate is 1 DEG C/min.Wait for that temperature is down to initial temperature, by earthenware Crucible takes out, and black solid is Fe3O4@cavitys@（The mesoporous layer of C-N nano-particles）Nano-particle；
（7）Take step（6）Gained Fe3O4@cavitys@（The mesoporous layer of C-N nano-particles）Nano-particle 0.2g and 1.0g hydroxide Sodium is dissolved in 100ml water, and ultrasonic disperse obtains uniform suspension for 30 minutes, is reacted 4 hours at 60 DEG C.Precipitation is divided by magnet From being washed with distilled water, at powder be Fe with mortar grinder dry 10 hours at 40 DEG C3O4@cavitys@（C-N nano-particles are situated between Aperture layer）Powder.
Embodiment 2：
（1）Six water of 1.8g ferric trichlorides, 2.0g anhydrous sodium acetates and 0.3g sodium citrates are dissolved in 50ml ethylene glycol, Ultrasonic disperse forms uniform suspension in 1 hour.By the suspension under room temperature mechanical agitation 2 hours, be added to 100ml later Reaction kettle in 180 DEG C react 12 hours.Precipitation is detached by magnet, uses the respectively washing 3 of absolute ethyl alcohol and distilled water successively It is secondary, it is 10 hours dry at 40 DEG C, obtain Fe3O4Nano-particle；
（2）120ml absolute ethyl alcohols and 8ml ammonium hydroxide are uniformly mixed, then 4ml ethyl orthosilicates were dripped in 20 minutes Finish, is reacted at 30 DEG C 10 hours, it is 12 hours dry at using absolute ethyl alcohol and distilled water respectively to wash 3 times, 40 DEG C successively, obtain SiO2 Nano-particle；
（3）By step（1）Gained Fe3O40.2g, 150ml absolute ethyl alcohol and 8ml ammonium hydroxide are mixed evenly, 20 DEG C of water-baths 5ml ethyl orthosilicates are slowly added dropwise after 50 minutes in lower mechanical agitation, continue mechanical agitation 12 hours, and solution slowly becomes white. Precipitation is detached by magnet, it is 10 hours dry at using absolute ethyl alcohol and distilled water respectively to wash 3 times, 40 DEG C successively, obtain Fe3O4@ SiO2Nano-particle；
（4）Take 37% formalin of 1.5g melamines and 4ml, magnetic agitation 40 minutes is complete to melamine at 60 DEG C Dissolving, obtains the mixed solution of homogeneous transparent；
（5）Take step（2）Gained SiO2Nano-particle 0.15g and 120ml distilled water be added after mixing it is above-mentioned dissolved with The formalin and 1.0g sodium hydroxides of melamine, mechanic whirl-nett reaction 1 hour under 60 DEG C of water-baths.Again by step（3）Institute Obtain Fe3O4@SiO2Nano-particle 0.1g is added in above-mentioned mixed solution, and the reaction was continued under the same terms 2 hours.It will by magnet Precipitation separation is washed with distilled water to drying 10 hours at lacking 3 times, 60 DEG C, obtains Fe3O4@SiO2@（SiO2It is multiple with melamine resin Close layer）Nano-particle；
（6）By step（5）Gained nano-particle mortar grinder is placed at powder in crucible, is trained using tube furnace It burns, condition is：Ar atmosphere is enclosed, 700 DEG C, keeps the temperature 5 hours, and heating rate is 1 DEG C/min.Wait for that temperature is down to initial temperature, by earthenware Crucible takes out, and black solid is Fe3O4@cavitys@（The mesoporous layer of C-N nano-particles）Nano-particle；
（7）Take step（6）Gained Fe3O4@cavitys@（The mesoporous layer of C-N nano-particles）Nano-particle 0.15g and 2ml hydrofluoric acid It is dissolved in 120ml water, ultrasonic disperse obtains uniform suspension for 40 minutes, is reacted 6 hours at 60 DEG C.Precipitation is divided by magnet From being washed with distilled water, at powder be Fe with mortar grinder dry 10 hours at 40 DEG C3O4@cavitys@（C-N nano-particles are situated between Aperture layer）Powder.
Embodiment 3：
（1）Six water of 2.5g ferric trichlorides, 3.0g anhydrous sodium acetates and 0.5g sodium citrates are dissolved in 60ml ethylene glycol, Ultrasonic disperse forms uniform suspension in 1 hour.By the suspension under room temperature mechanical agitation 1 hour, be added to 150ml later Reaction kettle in 200 DEG C react 10 hours.Precipitation is detached by magnet, uses the respectively washing 3 of absolute ethyl alcohol and distilled water successively It is secondary, it is 12 hours dry at 40 DEG C, obtain Fe3O4Nano-particle；
（2）150ml absolute ethyl alcohols and 15ml ammonium hydroxide are uniformly mixed, then 5ml ethyl orthosilicates were dripped in 30 minutes Finish, is reacted at 25 DEG C 12 hours, it is 12 hours dry at using absolute ethyl alcohol and distilled water respectively to wash 3 times, 40 DEG C successively, obtain SiO2 Nano-particle；
（3）By step（1）Gained Fe3O40.12g, 80ml absolute ethyl alcohol and 5ml ammonium hydroxide are mixed evenly, 25 DEG C of water-baths After sixty minutes, 4ml ethyl orthosilicates are slowly added dropwise in lower mechanical agitation, continue mechanical agitation 10 hours, and solution slowly becomes white. Precipitation is detached by magnet, it is 12 hours dry at using absolute ethyl alcohol and distilled water respectively to wash 3 times, 40 DEG C successively, obtain Fe3O4@ SiO2Nano-particle；
（4）Take 37% formalin of 2.3g melamines and 18ml, magnetic agitation 30 minutes is complete to melamine at 60 DEG C Fully dissolved obtains the mixed solution of homogeneous transparent；
（5）Take step（2）Gained SiO2Nano-particle 0.3g and 150ml distilled water are added above-mentioned dissolved with three after mixing The formalin and 2.5mL glacial acetic acids of poly cyanamid, mechanic whirl-nett reaction 1 hour under 60 DEG C of water-baths.Again by step（3）Gained Fe3O4@SiO2Nano-particle 0.15g is added in above-mentioned mixed solution, and the reaction was continued under the same terms 2 hours.It will be sunk by magnet It forms sediment and detaches, be washed with distilled water to drying 10 hours at lacking 3 times, 60 DEG C, obtain Fe3O4@SiO2@（SiO2It is compound with melamine resin Layer）Nano-particle；
（6）By step（5）Gained nano-particle mortar grinder is placed at powder in crucible, is trained using tube furnace It burns, condition is：Ar atmosphere is enclosed, 800 DEG C, keeps the temperature 6 hours, and heating rate is 1 DEG C/min.Wait for that temperature is down to initial temperature, by earthenware Crucible takes out, and black solid is Fe3O4@cavitys@（The mesoporous layer of C-N nano-particles）Nano-particle；
（7）Take step（6）Gained Fe3O4@cavitys@（The mesoporous layer of C-N nano-particles）Nano-particle 0.2g and 1.0g hydroxide Sodium is dissolved in 100ml water, and ultrasonic disperse obtains uniform suspension for 40 minutes, is reacted 5 hours at 80 DEG C.Precipitation is divided by magnet From being washed with distilled water, at powder be Fe with mortar grinder dry 12 hours at 40 DEG C3O4@cavitys@（C-N nano-particles are situated between Aperture layer）Powder.

Claims (5)

1. a kind of preparation method of lithium ion battery negative material, which is characterized in that include the following steps：
(1) six water of ferric trichloride, anhydrous sodium acetate and sodium citrate are uniformly mixed with a certain amount of ethylene glycol, are added to height It presses in reaction kettle, is reacted 10~12 hours at 180~200 DEG C, precipitation is detached by magnet, uses absolute ethyl alcohol and washing successively It washs, it is dry, obtain Fe3O4Nano-particle；
(2) absolute ethyl alcohol and ammonium hydroxide are uniformly mixed and obtain the first mixed solution, again by ethyl orthosilicate in 20 under mechanical agitation It is added dropwise in~30 minutes in above-mentioned first mixed solution, reacts at room temperature 10~12 hours, use absolute ethyl alcohol and washing successively It washs, it is dry, obtain SiO2Nano-particle；
(3) by Fe obtained by step (1)3O4Nano-particle, absolute ethyl alcohol and ammonium hydroxide are uniformly mixed, at 20~25 DEG C, mechanical agitation 30 ~a certain amount of ethyl orthosilicate is added dropwise after sixty minutes, precipitation is detached by magnet, is used successively by mechanical agitation 10~12 hours Absolute ethyl alcohol and water washing, it is dry, obtain Fe3O4@SiO2Nano-particle；
(4) melamine under 50~60 DEG C of water-baths is dissolved in 37% formalin, obtains the mixed solution of homogeneous transparent；
(5) by SiO obtained by step (2)2Nano-particle and water are uniformly mixed, and gained mixed solution and catalysis in step (4) is added Agent obtains the second mixed solution after being reacted 0.5~3 hour under 50~60 DEG C of water-baths, by Fe obtained by step (3)3O4@SiO2It receives Rice corpuscles is added in above-mentioned second mixed solution, and continuation is reacted 2~4 hours under 50~60 DEG C of water bath conditions, will by magnet Precipitation separation, is washed with water, dry, obtains Fe3O4@SiO2@“SiO2Nano-particle and melamine resin composite layer " nano-particle；
(6) obtained solid product in step (5) is sintered 4~6 hours in 600~850 DEG C of inert gas shielding atmosphere, is obtained Fe3O4@SiO2@“SiO2With C-N composite layers "；
(7) by gained Fe in step (6)3O4@SiO2@“SiO2With C-N composite layers " nano-particle solid product, etching agent and water into Row mixing, reacts 4~8 hours at 60~85 DEG C, detaches precipitation by magnet, is washed with water, dry, obtains Fe3O4@is empty Chamber@" the mesoporous layer of C-N nano-particles " nano-particle.
2. a kind of preparation method of lithium ion battery negative material as described in claim 1, it is characterised in that：The step (4) molar ratio of melamine and 37% formalin is 1:1~5.
3. a kind of preparation method of lithium ion battery negative material as described in claim 1, it is characterised in that：The step (5) catalyst is one kind in formic acid, glacial acetic acid or sodium hydroxide.
4. a kind of preparation method of lithium ion battery negative material as described in claim 1, it is characterised in that：The step (7) etching agent is one kind in hydrofluoric acid or sodium hydroxide.
5. a kind of preparation method of lithium ion battery negative material as described in claim 1, it is characterised in that：The step (7) Fe3O4@cavitys@" the mesoporous layer of C-N nano-particles " nano-particle, shell contain etching after formed it is mesoporous.
CN201610151315.5A 2016-03-17 2016-03-17 A kind of preparation method of lithium ion battery negative material Expired - Fee Related CN105552354B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610151315.5A CN105552354B (en) 2016-03-17 2016-03-17 A kind of preparation method of lithium ion battery negative material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610151315.5A CN105552354B (en) 2016-03-17 2016-03-17 A kind of preparation method of lithium ion battery negative material

Publications (2)

Publication Number Publication Date
CN105552354A CN105552354A (en) 2016-05-04
CN105552354B true CN105552354B (en) 2018-09-18

Family

ID=55831415

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610151315.5A Expired - Fee Related CN105552354B (en) 2016-03-17 2016-03-17 A kind of preparation method of lithium ion battery negative material

Country Status (1)

Country Link
CN (1) CN105552354B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102132239B1 (en) * 2018-11-21 2020-07-09 (주)파마오넥스 Method for manufacturing porous silica-iron-copper

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113543616A (en) * 2021-07-16 2021-10-22 中原工学院 Hollow core-shell structure Fe3O4@SiO2@ PANI wave absorbing agent and preparation method thereof
CN113636563B (en) * 2021-08-24 2023-12-22 郑州轻工业大学 SiO (silicon dioxide) 2 Preparation method of incompletely coated magnetic nano particles

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103182294B (en) * 2013-03-27 2014-09-17 哈尔滨工业大学 Method for preparing magnetic mesoporous carbon nanoparticles with high adsorption property for dyes under acidic condition
CN104415741B (en) * 2013-09-10 2017-04-12 中国科学院大连化学物理研究所 Composite nanometer material with core-shell structure, preparation method and application of composite nanometer material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102132239B1 (en) * 2018-11-21 2020-07-09 (주)파마오넥스 Method for manufacturing porous silica-iron-copper

Also Published As

Publication number Publication date
CN105552354A (en) 2016-05-04

Similar Documents

Publication Publication Date Title
CN105565265B (en) A kind of preparation method of the complex microsphere lithium ion battery negative material with yolk structure
CN104810509B (en) Ferroso-ferric oxide/graphene three dimensional composite structure and its preparation method and application
CN104852026B (en) Core-shell polynary lithium ion battery anode material distributed in all-concentration gradient way and preparation method thereof
CN102255079B (en) Stannum-carbon composite material used for lithium ion battery cathode, preparation method thereof and lithium ion battery
CN108373175A (en) Aluminium doped cobaltic-cobaltous oxide and its preparation method and application
CN102437318A (en) Preparation method for silicon-carbon composite material, prepared silicon-carbon composite material, lithium ion battery anode containing silicon-carbon composite material and battery
CN112349899B (en) Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery
CN102881871A (en) Method for preparing graphite/silicone composite material for negative electrode of lithium ion battery
CN107293713A (en) A kind of super-low-temperature lithium-ion cell composite positive pole and preparation method thereof
CN102824884B (en) A kind of TiO 2/ Fe 2o 3compound hollow microballoon and preparation method thereof
CN105552354B (en) A kind of preparation method of lithium ion battery negative material
CN109449420A (en) A kind of surface low-level oxidation and liquid phase coating modified graphite cathode material and preparation method thereof
CN105870425A (en) Sodium-ion battery carbon negative electrode material and preparation method thereof
CN103204490B (en) Preparation method of iron trioxide/carbon yolk-eggshell nano-composite structure
CN103259018A (en) Preparation method of porous graphite flake applied to super-electric negative pole of lithium battery
CN104692468A (en) Preparation method of three-dimensional multiwall hollow sphere NiO nano material
CN108270001A (en) " one kettle way " synthesizes the preparation method of ferroso-ferric oxide@carbon composites
CN103078120B (en) Ferrous silicate lithium ion battery cathode material with hierarchical structure and preparation method
CN113104852A (en) Preparation method of silicon-carbon negative electrode material of lithium ion battery
CN101367526B (en) Preparation method for Ce3<+> doping lutetium silicate polycrystal luminescent powder
CN106784803A (en) A kind of cobalt acid nickel nanocube material and its preparation method and application
CN109516504A (en) A kind of porous hexa-prism pyrovanadic acid cobalt and its preparation method and application
CN105271443A (en) Method for preparing flaky nano CoO or Co3O4 through assistant microwave heating
CN108467066A (en) A kind of porous micro-nano structure ZnMn of rice-shaped2O4Lithium ion battery negative material
CN106848289A (en) One species lotus root sheet spinel-type ZnMn2O4Raw powder's production technology

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180918

Termination date: 20190317

CF01 Termination of patent right due to non-payment of annual fee