CN104393244B - Preparation method of hollow ZnFe2O4 nanometer anode material of lithium ion battery - Google Patents

Preparation method of hollow ZnFe2O4 nanometer anode material of lithium ion battery Download PDF

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CN104393244B
CN104393244B CN201410707056.0A CN201410707056A CN104393244B CN 104393244 B CN104393244 B CN 104393244B CN 201410707056 A CN201410707056 A CN 201410707056A CN 104393244 B CN104393244 B CN 104393244B
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zinc
lithium ion
ion battery
mixed solution
anode material
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CN104393244A (en
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廖丽霞
方涛
陈立钢
王明
刘光跃
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Northeast Forestry University
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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

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  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a preparation method of a hollow ZnFe2O4 nanometer anode material of a lithium ion battery, and relates to a preparation method of an anode material of a lithium ion battery. The invention aims to solve the problems that an existing ZnFe2O4 nanometer anode material of a lithium ion battery is powdered and the cycle performance is greatly reduced because the volume of the anode material is rapidly changed due to phase change of a material structure in a long-term cycle process. The preparation method comprises the following steps: 1, preparing sugar particles; 2, preparing carbon microspheres; 3, preparing a carbon microsphere turbid liquid; 4, preparing a zinc-ferric mixed solution; 5, preparing a zinc-ferric-ethylene glycol-urea mixed solution; 6, preparing a blend; 7, preparing nanometer spinel ZnFe2O4 powder; and 8, sintering to obtain the hollow ZnFe2O4 nanometer anode material of the lithium ion battery. The hollow ZnFe2O4 nanometer anode material of the lithium ion battery, prepared by adopting the preparation method, is used as an electrode material of the lithium ion battery.

Description

Lithium ion battery hollow ZnFe2O4The preparation method of nanometer anode material
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material.
Background technology
The contradiction of energy demand and change that the increasingly depleted of the non-renewable energy resources such as oil, coal and the mankind grow with each passing day The considerable damage that the dusty gass that stone fuel produces cause to environment, leads to current global warming, disease to be wreaked havoc and natural disaster Frequently occur, promote people to seek the alternative energy source of clean environment firendly.As a kind of efficient clean energy resource, lithium ion battery has Energy density is high, memory-less effect and the strong feature of cyclical stability, has become as the indispensable composition of a large amount of electronic products Part it is even more important that lithium ion battery very likely petroleum replacing becomes the power source of power vehicle.
The design of negative material and preparation are the keys obtaining high performance lithium ion secondary battery.At present business-like lithium from Using material with carbon element cell negative electrode material more, the formation of " Li dendrite " in charge and discharge process, easily cause battery short circuit and cause Blast, and the theoretical capacity of graphite-like material with carbon element is only 372mAh/g, therefore find security performance more preferably, specific capacity is higher, follow Ring life-span longer novel anode material, it has also become the focus of Study on Li-ion batteries.Composite transition metal oxide material can With the electro-chemical activity of integrated use each single transition metal oxide, the running voltage of Effective Regulation battery and reversible capacity, Probably become high-energy-density, the lithium ion battery with high specific power negative material of great potential of future generation.Wherein ZnFe2O4With Multiple storage lithium mechanism are simultaneously deposited, and show excellent storage lithium performance, however, due to ZnFe2O4Low conductivity and material structure phase The impact becoming, in long-term cyclic process, so that material efflorescence, cycle performance significantly declines for the drastically change of material volume.
Content of the invention
The invention aims to solving existing ZnFe2O4Lithium ion battery negative material material in long-term cyclic process Structural phase transition causes material volume drastically to change so that material efflorescence, the problem that cycle performance significantly declines, and provide lithium from Sub- battery hollow ZnFe2O4The preparation method of nanometer anode material.
Lithium ion battery hollow ZnFe2O4The preparation method of nanometer anode material, is specifically carried out according to the following steps：
First, prepare sugared granule：Will be soluble in water for sugar, and magnetic agitation mixes, obtaining concentration is 0.5mol/L～2.0mol/ L homogeneously mixes sugar juice, is then spray-dried at temperature is 180 DEG C, obtains sugared granule；
2nd, prepare carbosphere：Sugared granule is placed in tube furnace, under nitrogen protection with heating rate for 1 DEG C/min～3 DEG C/min from room temperature to 500 DEG C, then with heating rate for 5 DEG C/min～10 DEG C/min from temperature be under nitrogen protection 500 DEG C are warming up to 700 DEG C～1200 DEG C, take out, obtain carbosphere after cooling to room temperature with the furnace；
3rd, prepare carbosphere suspension：Carbosphere is added in distilled water, and magnetic agitation 2h～4h, obtain carbosphere Suspension；The quality of the carbosphere described in step 3 and the volume ratio of distilled water are 1g:(20mL～30mL)；
4th, prepare zinc-iron mixed solution：Zinc source compound and Fe source compound are sequentially added in solvent, stirs to zinc Source compound and Fe source compound are completely dissolved, and obtain zinc-iron mixed solution；In zinc-iron mixed solution described in step 4 Zn2+With Fe3+Mol ratio be 1:2；The quality of zinc source compound described in step 4 is 1g with the volume ratio of solvent: (120mL～180mL)；
5th, prepare zinc-ferrum-ethylene glycol-carbamide mixed solution：Add ethylene glycol and carbamide in zinc-iron mixed solution, and Magnetic agitation 2h～4h, obtains zinc-ferrum-ethylene glycol-carbamide mixed solution；Zinc in zinc-iron mixed solution described in step 5 The quality of source compound and the volume ratio of ethylene glycol are 1g:(200mL～250mL)；Zinc-iron mixed solution described in step 5 Middle zinc source compound is 1 with the mass ratio of carbamide:(4～5)；
6th, prepare blend：Carbosphere suspension is mixed with zinc-ferrum-ethylene glycol-carbamide mixed solution, and magnetic force stirs Mix mixing, obtain blend；Carbosphere suspension described in step 6 and the volume of zinc-ferrum-ethylene glycol-carbamide mixed solution Than for 1:(4～6)；
7th, prepare nanometer spinel type ZnFe2O4Powder：Blend is transferred in reactor, and temperature be 180～ React 12h～48h at 240 DEG C, take out after being cooled to room temperature, then filtered or Magnetic Isolation, obtain solid product, first Using distilled water, solid product is cleaned 3～6 times, then using ethanol purge 3～6 times, be finally 40～80 DEG C of vacuum in temperature 4h～8h is dried in drying baker, obtains nanometer spinel type ZnFe2O4Powder；
8th, sinter：By nanometer spinel type ZnFe2O4Powder is placed in Muffle furnace, burns at temperature is 500～800 DEG C Knot 3h～5h, obtains lithium ion battery hollow ZnFe2O4Nanometer anode material.
Advantage of the present invention：First, lithium ion hollow ZnFe of the inventive method synthesis2O4Nanometer anode material has excellent Chemical property, first discharge capacity can reach 1000mAh g-1More than, charging capacity is 950mAh g-1More than, its coulomb Efficiency reaches more than 85%, during following cycle, and reversible capacity can maintain 930mAh g-1Left and right, with 50mA g-1's After current cycle 50 times, its reversible capacity still can keep 790mAh g-1Left and right, is 2 times of conventional graphite class Carbon Materials capacity More than, and capability retention reaches 80% about, using lithium ion battery hollow ZnFe of present invention preparation2O4Nanometer negative pole material Material has excellent stable circulation performance and higher specific capacity.2nd, lithium ion battery hollow ZnFe of present invention preparation2O4Receive Rice negative material has special construction (nanoscale hollow structure), and nanometer particle size can improve the contact energy between electrode and electrolyte Power, hollow structure can improve the reversible deintercalation speed of lithium ion, and the volumetric expansion that effectively produces in buffering course of reaction and Shrink.The material that this preparation method obtains is expected to promote high power capacity, high circulation stability electrokinetic cell in power vehicle, high-energy Application process on energy storage device etc..
Brief description
Fig. 1 is lithium ion battery hollow ZnFe of test one preparation2O4The XRD spectrum of nanometer anode material；
Fig. 2 is lithium ion battery hollow ZnFe of test one preparation2O4The SEM figure of nanometer anode material；
Fig. 3 is lithium ion battery hollow ZnFe of test one preparation2O4The TEM figure of nanometer anode material；
Fig. 4 is the charging and discharging curve figure of the CR2025 type battery front ten times of test two preparation；In figure A represents first time charge and discharge Electric curve chart, in figure B represents second charging and discharging curve figure, and in figure C represents third time charging and discharging curve figure, and in figure D represents Four charging and discharging curve figures, in figure E represents the 5th charging and discharging curve figure, and in figure F represents the tenth charging and discharging curve figure；
Fig. 5 is the CR2025 type cycle performance of battery figure of test two preparation, in figure ▲ expression discharge curve, in figure table Show charge graph.
Specific embodiment
Specific embodiment one：Present embodiment is lithium ion battery hollow ZnFe2O4The preparation side of nanometer anode material Method, is specifically carried out according to the following steps：
First, prepare sugared granule：Will be soluble in water for sugar, and magnetic agitation mixes, obtaining concentration is 0.5mol/L～2.0mol/ L homogeneously mixes sugar juice, is then spray-dried at temperature is 180 DEG C, obtains sugared granule；
2nd, prepare carbosphere：Sugared granule is placed in tube furnace, under nitrogen protection with heating rate for 1 DEG C/min～3 DEG C/min from room temperature to 500 DEG C, then with heating rate for 5 DEG C/min～10 DEG C/min from temperature be under nitrogen protection 500 DEG C are warming up to 700 DEG C～1200 DEG C, take out, obtain carbosphere after cooling to room temperature with the furnace；
3rd, prepare carbosphere suspension：Carbosphere is added in distilled water, and magnetic agitation 2h～4h, obtain carbosphere Suspension；The quality of the carbosphere described in step 3 and the volume ratio of distilled water are 1g:(20mL～30mL)；
4th, prepare zinc-iron mixed solution：Zinc source compound and Fe source compound are sequentially added in solvent, stirs to zinc Source compound and Fe source compound are completely dissolved, and obtain zinc-iron mixed solution；In zinc-iron mixed solution described in step 4 Zn2+With Fe3+Mol ratio be 1:2；The quality of zinc source compound described in step 4 is 1g with the volume ratio of solvent: (120mL～180mL)；
5th, prepare zinc-ferrum-ethylene glycol-carbamide mixed solution：Add ethylene glycol and carbamide in zinc-iron mixed solution, and Magnetic agitation 2h～4h, obtains zinc-ferrum-ethylene glycol-carbamide mixed solution；Zinc in zinc-iron mixed solution described in step 5 The quality of source compound and the volume ratio of ethylene glycol are 1g:(200mL～250mL)；Zinc-iron mixed solution described in step 5 Middle zinc source compound is 1 with the mass ratio of carbamide:(4～5)；
6th, prepare blend：Carbosphere suspension is mixed with zinc-ferrum-ethylene glycol-carbamide mixed solution, and magnetic force stirs Mix mixing, obtain blend；Carbosphere suspension described in step 6 and the volume of zinc-ferrum-ethylene glycol-carbamide mixed solution Than for 1:(4～6)；
7th, prepare nanometer spinel type ZnFe2O4Powder：Blend is transferred in reactor, and temperature be 180～ React 12h～48h at 240 DEG C, take out after being cooled to room temperature, then filtered or Magnetic Isolation, obtain solid product, First adopt distilled water that solid product is cleaned 3～6 times, then using ethanol purge 3～6 times, finally temperature be 40～80 DEG C true 4h～8h is dried in empty drying baker, obtains nanometer spinel type ZnFe2O4Powder；
8th, sinter：By nanometer spinel type ZnFe2O4Powder is placed in Muffle furnace, burns at temperature is 500～800 DEG C Knot 3h～5h, obtains lithium ion battery hollow ZnFe2O4Nanometer anode material.
In zinc-ferrum-ethylene glycol-carbamide mixed solution in present embodiment step 5, liquid composition only has described in step 4 Solvent and step 5 described in ethylene glycol, when ethylene glycol accounts for more than the 50% of ethylene glycol and total solvent volume, prepared Material particle size be 200nm, and even particle size distribution, therefore ethylene glycol play pivotal role to the particle diameter preparing material, In the zinc-ferrum-ethylene glycol-carbamide mixed solution obtaining in present embodiment step 5, ethylene glycol accounts for ethylene glycol and total solvent volume 50%～100%.
Specific embodiment two：The difference from specific embodiment one for the present embodiment is：Sugar described in step one For glucose or sucrose.Other are identical with specific embodiment one.
Specific embodiment three：Present embodiment with one of specific embodiment one or two difference is：Institute in step 4 The zinc source compound stated is zinc chloride, zinc acetate or zinc sulfate.Other are identical with specific embodiment one or two.
Specific embodiment four：Present embodiment with one of specific embodiment one to three difference is：Institute in step 4 The Fe source compound stated is iron chloride, iron acetate or iron sulfate.Other are identical with specific embodiment one to three.
Specific embodiment five：Present embodiment with one of specific embodiment one to four difference is：Institute in step 4 The solvent stated is distilled water, ethylene glycol or ethylene glycol-distillation aqueous mixtures.Other are identical with specific embodiment one to four.
Solvent described in when present embodiment is ethylene glycol-distillation aqueous mixtures, and ethylene glycol-distillation aqueous mixtures are by second two Alcohol and distilled water are mixed by any ratio and form.
Specific embodiment six：Present embodiment with one of specific embodiment one to five difference is：Institute in step 5 In the zinc-iron mixed solution stated, the quality of zinc source compound and the volume ratio of ethylene glycol are 1g:(200mL～240mL).Other with Specific embodiment one to five is identical.
Specific embodiment seven：Present embodiment with one of specific embodiment one to six difference is：Institute in step 5 In the zinc-iron mixed solution stated, zinc source compound and the mass ratio of carbamide are 1:(4～4.8).Other are with specific embodiment one Identical to six.
Specific embodiment eight：Present embodiment with one of specific embodiment one to seven difference is：Institute in step 6 The carbosphere suspension stated is 1 with the volume ratio of zinc-ferrum-ethylene glycol-carbamide mixed solution:(4.2～5.8).Other with concrete Embodiment one to seven is identical.
Using following verification experimental verifications effect of the present invention
Test one：Lithium ion battery hollow ZnFe2O4The preparation method of nanometer anode material, specifically enters according to the following steps Row：
First, prepare sugared granule：Glucose is soluble in water, and magnetic agitation mixing, obtaining concentration is that 0.5mol/L is homogeneous Mixing sugar juice, is then spray-dried at temperature is 180 DEG C, is obtained sugared granule；
2nd, prepare carbosphere：Sugared granule is placed in tube furnace, under nitrogen protection with heating rate for 1 DEG C/min from Room temperature, to 500 DEG C, is then warming up to 1000 DEG C from temperature for 500 DEG C for 5 DEG C/min with heating rate under nitrogen protection, Take out after cooling to room temperature with the furnace, obtain carbosphere；
3rd, prepare carbosphere suspension：Carbosphere is added in distilled water, and magnetic agitation 2h, obtain carbosphere suspended Liquid；The quality of the carbosphere described in step 3 and the volume ratio of distilled water are 1g:20mL；
4th, prepare zinc-iron mixed solution：Zinc source compound and Fe source compound are sequentially added in distilled water, stir to Zinc source compound and Fe source compound are completely dissolved, and obtain zinc-iron mixed solution；Zinc-iron mixed solution described in step 4 Middle Zn2+With Fe3+Mol ratio be 1:2；The quality of zinc source compound described in step 4 is 1g with the volume ratio of distilled water: 150mL；
5th, prepare zinc-ferrum-ethylene glycol-carbamide mixed solution：Add ethylene glycol and carbamide in zinc-iron mixed solution, and Magnetic agitation 3h, obtains zinc-ferrum-ethylene glycol-carbamide mixed solution；Zinc source in zinc-iron mixed solution described in step 5 The quality of compound and the volume ratio of ethylene glycol are 1g:250mL；Zinc source compound in zinc-iron mixed solution described in step 5 Mass ratio with carbamide is 1:4；
6th, prepare blend：Carbosphere suspension is mixed with zinc-ferrum-ethylene glycol-carbamide mixed solution, and magnetic force stirs Mix mixing, obtain blend；Carbosphere suspension described in step 6 and the volume of zinc-ferrum-ethylene glycol-carbamide mixed solution Than for 1:5；
7th, prepare nanometer spinel type ZnFe2O4Powder：Blend is transferred in reactor, and is 180 DEG C in temperature Lower reaction 12h, takes out after being cooled to room temperature, then carries out Magnetic Isolation, obtain solid product, first adopts distilled water that solid is produced Thing cleans 6 times, then using ethanol purge 6 times, is finally 8h to be dried in 40 DEG C of vacuum drying ovens in temperature, obtains nano spinel Type ZnFe2O4Powder；
8th, sinter：By nanometer spinel type ZnFe2O4Powder is placed in Muffle furnace, sinters 3h at temperature is 500 DEG C, Obtain lithium ion battery hollow ZnFe2O4Nanometer anode material.
The nanometer spinel type ZnFe of this test procedure seven preparation2O4Powder has magnetic, nanometer spinel type ZnFe2O4 Powder, in the effect of Magnet, is close to walls of beaker, takes Magnetic Isolation, reduces loss in centrifuge washing for the material, also adds simultaneously The fast preparation process of material.
Lithium ion battery hollow ZnFe to this test preparation2O4Nanometer anode material is detected, testing result such as Fig. 1 Shown, Fig. 1 is lithium ion battery hollow ZnFe of test one preparation2O4The XRD spectrum of nanometer anode material, as shown in Figure 1 originally Lithium ion battery hollow ZnFe of test preparation2O4Nanometer anode material has preferable degree of crystallinity, and all of diffraction maximum all belongs to ZnFe in cubic spinel structure2O4, corresponding to JCPDS card number 01-1109.
Lithium ion battery hollow ZnFe to this test preparation2O4Nanometer anode material is observed, observed result such as Fig. 2 With shown in 3, Fig. 2 is lithium ion battery hollow ZnFe of test one preparation2O4The SEM figure of nanometer anode material, Fig. 3 is test one Lithium ion battery hollow ZnFe of preparation2O4Nanometer anode material TEM figure, as can be seen from Figure 2 this test prepare lithium from Sub- battery hollow ZnFe2O4Nanometer anode material granule is uniform, mean diameter about 150nm about, and particle surface has many holes Gap.As seen from Figure 3, lithium ion battery hollow ZnFe of this test preparation2O4Nanometer anode material has nanoscale hollow knot Structure.
Test two：Using lithium ion battery hollow ZnFe2O4The method that nanometer anode material prepares battery, specifically press with Lower step completes：
First, prepare ZnFe2O4Electrode：With lithium ion battery hollow ZnFe2O4Nanometer anode material is active substance, conductive Agent is acetylene black, and binding agent is Kynoar (PVDF), prepares ZnFe2O4Electrode；2nd, assemble：With ZnFe2O4Electrode conduct Negative pole, is to electrode with metal lithium sheet, with the LiPF containing 1mol/L6EC (ethylene carbonate)-DEC (diethyl carbonate)-DMC (dimethyl carbonate) solution is electrolyte, and polypropylene porous film is barrier film, is assembled into CR2025 type battery.Can by charging and discharging curve Know, when discharging first, its capacity can reach 1150.2mAh g-1, charging capacity is 996.5mAh g-1, its coulombic efficiency is 86.6%, during following cycle, reversible capacity can maintain 930.9mAh g-1.
Under the conditions of discharge and recharge is interval for 0.01V～3.0V, the discharge and recharge for 50mA/g for the charging and discharging currents, testing experiment two The cycle performance of the CR2025 type battery of preparation；Test result is as shown in figure 4, Fig. 4 is the CR2025 type battery of test two preparation The charging and discharging curve figure of front ten times, in figure A represents first time charging and discharging curve figure, and in figure B represents second charging and discharging curve figure, In figure C represents third time charging and discharging curve figure, and in figure D represents the 4th charging and discharging curve figure, and in figure E represents the 5th discharge and recharge Curve chart, in figure F represents the tenth charging and discharging curve figure；As shown in Figure 4, when discharging first, its capacity can reach 1150.2mAh/g, charging capacity is 996.5mAh/g, and its coulombic efficiency is 86.6%, and during following cycle, reversible capacity can To maintain 930.9mAh/g.
The CR2025 type batteries of test two preparation, with the current cycle 50 times of 50mA/g, obtain cycle performance figure such as Fig. 5 institute Show, Fig. 5 is the CR2025 type cycle performance of battery figure of test two preparation, in figure ▲ expression discharge curve, and in figure represents fills Electric curve chart；As shown in Figure 5, after circulating 50 times, the CR2025 type battery reversible capacities of test two preparation still can keep 792.7mAh/g, its reversible capacity conservation rate is 79.5%, illustrates that the CR2025 type battery testing two preparations has excellent following Ring stability.Prove lithium ion battery hollow ZnFe using present invention preparation2O4The electrode of nanometer anode material preparation is as lithium Ion battery electrode has excellent stable circulation performance.

Claims (7)

1. lithium ion battery hollow ZnFe2O4The preparation method of nanometer anode material is it is characterised in that lithium ion battery hollow ZnFe2O4The preparation method of nanometer anode material is carried out according to the following steps：
First, prepare sugared granule：Will be soluble in water for sugar, and magnetic agitation mixes, obtaining concentration is that 0.5mol/L～2.0mol/L is equal Mutually mix sugar juice, be then spray-dried at temperature is 180 DEG C, obtain sugared granule；
Sugar described in step one is glucose or sucrose；
2nd, prepare carbosphere：Sugared granule is placed in tube furnace, under nitrogen protection with heating rate for 1 DEG C/min～3 DEG C/ Min from room temperature to 500 DEG C, then under nitrogen protection with heating rate for 5 DEG C/min～10 DEG C/min from temperature be 500 DEG C it is warming up to 700 DEG C～1200 DEG C, take out after cooling to room temperature with the furnace, obtain carbosphere；
3rd, prepare carbosphere suspension：Carbosphere is added in distilled water, and magnetic agitation 2h～4h, obtain carbosphere suspended Liquid；The quality of the carbosphere described in step 3 and the volume ratio of distilled water are 1g：(20mL～30mL)；
4th, prepare zinc-iron mixed solution：Zinc source compound and Fe source compound are sequentially added in solvent, stirs to zinc source Compound and Fe source compound are completely dissolved, and obtain zinc-iron mixed solution；Zn in zinc-iron mixed solution described in step 42+With Fe3+Mol ratio be 1:2；The quality of zinc source compound described in step 4 is 1g with the volume ratio of solvent：(120mL～ 180mL)；
5th, prepare zinc-ferrum-ethylene glycol-carbamide mixed solution：Add ethylene glycol and carbamide in zinc-iron mixed solution, and magnetic force Stirring 2h～4h, obtains zinc-ferrum-ethylene glycol-carbamide mixed solution；Zinc source in zinc-iron mixed solution described in step 5 The quality of compound and the volume ratio of ethylene glycol are 1g：(200mL～250mL)；Zinc in zinc-iron mixed solution described in step 5 Source compound is 1 with the mass ratio of carbamide：(4～5)；
6th, prepare blend：Carbosphere suspension is mixed with zinc-ferrum-ethylene glycol-carbamide mixed solution, and magnetic agitation is mixed Even, obtain blend；Carbosphere suspension described in step 6 with the volume ratio of zinc-ferrum-ethylene glycol-carbamide mixed solution is 1：(4～6)；
7th, prepare nanometer spinel type ZnFe2O4Powder：Blend is transferred in reactor, and is 180～240 DEG C in temperature Lower reaction 12h～48h, takes out after being cooled to room temperature, is then filtered or Magnetic Isolation, obtain solid product, first adopt Distilled water cleans 3～6 times to solid product, then using ethanol purge 3～6 times, is finally 40～80 DEG C of vacuum drying in temperature 4h～8h is dried in case, obtains nanometer spinel type ZnFe2O4Powder；
8th, sinter：By nanometer spinel type ZnFe2O4Powder is placed in Muffle furnace, sinters 3h at temperature is 500～800 DEG C ～5h, obtains lithium ion battery hollow ZnFe2O4Nanometer anode material.
2. lithium ion battery hollow ZnFe according to claim 12O4The preparation method of nanometer anode material, its feature exists Zinc source compound described in step 4 is zinc chloride, zinc acetate or zinc sulfate.
3. lithium ion battery hollow ZnFe according to claim 12O4The preparation method of nanometer anode material, its feature exists Fe source compound described in step 4 is iron chloride, iron acetate or iron sulfate.
4. lithium ion battery hollow ZnFe according to claim 12O4The preparation method of nanometer anode material, its feature exists Solvent described in step 4 is distilled water, ethylene glycol or ethylene glycol-distillation aqueous mixtures.
5. lithium ion battery hollow ZnFe according to claim 12O4The preparation method of nanometer anode material, its feature exists In zinc-iron mixed solution described in step 5, the quality of zinc source compound and the volume ratio of ethylene glycol are 1g：(200mL～ 240mL).
6. lithium ion battery hollow ZnFe according to claim 12O4The preparation method of nanometer anode material, its feature exists In zinc-iron mixed solution described in step 5, zinc source compound and the mass ratio of carbamide are 1：(4～4.8).
7. lithium ion battery hollow ZnFe according to claim 12O4The preparation method of nanometer anode material, its feature exists Carbosphere suspension described in step 6 is 1 with the volume ratio of zinc-ferrum-ethylene glycol-carbamide mixed solution：(4.2～ 5.8).
CN201410707056.0A 2014-11-28 2014-11-28 Preparation method of hollow ZnFe2O4 nanometer anode material of lithium ion battery Expired - Fee Related CN104393244B (en)

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