CN105914357B - A kind of preparation method of the lithium titanate anode material for lithium ion battery of iron content and potassium - Google Patents

A kind of preparation method of the lithium titanate anode material for lithium ion battery of iron content and potassium Download PDF

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CN105914357B
CN105914357B CN201610452474.9A CN201610452474A CN105914357B CN 105914357 B CN105914357 B CN 105914357B CN 201610452474 A CN201610452474 A CN 201610452474A CN 105914357 B CN105914357 B CN 105914357B
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lithium
source
potassium
iron
solution
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CN105914357A (en
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丁克强
赵棉
赵婧
张燕
魏斌娟
王庆飞
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Hebei Normal 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
    • H01M4/362—Composites
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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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Abstract

A kind of preparation method of the lithium titanate anode material for lithium ion battery of iron content and potassium, including：One kind in titanium dioxide and butyl titanate is chosen as titanium source, lithium acetate, one kind in lithium carbonate and lithium hydroxide is as lithium source, the potassium ferricyanide, one kind in iron oxide and ferric nitrate is as source of iron, one kind in potassium nitrate and potassium carbonate is as potassium resource, by lithium source, titanium source, source of iron and potassium resource are weighed respectively by the amount ratio of material, afterwards, by lithium source, source of iron and potassium resource are dissolved in the mixed aqueous solution that deionized water forms three, at the same time, titanium source is dissolved in absolute ethyl alcohol and forms ethanol solution, ethanol solution is added dropwise in mixed aqueous solution again, stirring forms yellow gum solution, obtained yellow gum solution is dried, obtain presoma, presoma is ground, after tabletting, the high-temperature calcination in Muffle furnace is placed in crucible, obtain the lithium titanate anode material for lithium ion battery of iron content and potassium.Prepared material has high specific discharge capacity and more preferable cyclical stability.

Description

A kind of preparation method of the lithium titanate anode material for lithium ion battery of iron content and potassium
Technical field
The present invention relates to the preparation method of lithium ion battery material, particularly a kind of lithium ion battery titanium containing iron and potassium The preparation method of sour lithium titanate cathode material, belongs to technical field of energy material.
Background technology
Lithium ion battery is because with high specific energy and energy density per unit volume, having extended cycle life, can fill and pollution-free, nothing The advantages that memory effect, obtained universal application in portable electric appts and electric automobile.At present, commercially with lithium from The negative material of sub- battery is mainly carbon material.Research finds, due to the current potential of carbon material and the current potential of lithium metal very close to, when During over-charging of battery, elemental lithium can separate out in carbon material surface and form Li dendrite, can cause short circuit under certain condition, trigger peace Full problem.Explored to improve the security of lithium ion battery and other chemical properties, people comprising nitride, silicon Many new lithium cell cathode materials including sill, tin-based material, various novel alloys.In numerous negative materials In, lithium titanate（Li4Ti5O12）Because " zero strain " that own vol is shown when having higher charging/discharging voltage and discharge and recharge is special Property, it is considered to be most one of lithium cell cathode material of development potentiality.With going deep into for related lithium titanate material research, people Find lithium titanate electrical conductivity and ion diffusion coefficient it is all relatively low, in high power charging-discharging, capacity attenuation is quickly.In order to Overcome these deficiencies of lithium titanate, metal oxide, carbon material and various metal simple-substances are doped in lithium titanate by people, the phase Hoping improves the chemical property of lithium titanate.Literature survey shows there is researcher using the compound of the iron content such as ferric nitrate as source of iron, system It is standby gone out the lithium titanate of Fe2O3 doping.Research is found, a certain amount of iron is adulterated in lithium titanate, can improve the capacity of lithium titanate, but Capacity retention ratio is still relatively low.Therefore, it is still one of current scientific research task to develop new lithium titanate material.
The content of the invention
It is an object of the invention to provide a kind of iron content and the preparation method of the lithium titanate anode material for lithium ion battery of potassium, Under the same conditions, the lithium battery prepared has the discharge capacity of higher and more preferable cycle performance.
The iron content and the preparation method of the lithium titanate anode material for lithium ion battery of potassium that the present invention provides, including following step Suddenly：
（1）The preparation of material
It is Li by the amount ratio that lithium source, titanium source, source of iron and potassium resource press material:Ti:Fe：K=(0.3~2.0):1:(0~0.5)： （0~0.6）Ratio weighed respectively；
（2）The formation of colloidal solution
Lithium source, source of iron and potassium resource are dissolved in the mixed aqueous solution A that three is formed in deionized water, meanwhile, titanium source is dissolved in Ethanol solution B is formed in absolute ethyl alcohol, then solution B is added dropwise in solution A, magnetic stirrer 0.1~2.5h shapes Yellowly colloidal solution；
（3）Drying and calcining
Obtained yellow gum solution is placed in air dry oven at 40~200 DEG C dry 1~8h, obtains forerunner Body, presoma is ground in agate mortar, after tabletting, is placed in crucible in Muffle furnace at a temperature of 400~900 DEG C, is forged Burn 4~15h, you can obtain the lithium titanate anode material of iron content and potassium.
The method of the present invention, raw material lithium source is lithium carbonate, one kind in lithium acetate, lithium hydroxide.
The method of the present invention, raw material titanium source is butyl titanate, one kind in titanium dioxide.
The method of the present invention, raw material source of iron is the potassium ferricyanide, one kind in iron oxide, ferric nitrate.
The method of the present invention, raw material potassium resource are one kind in potassium nitrate and potassium carbonate.
What the present invention obtained has the beneficial effect that：A certain amount of iron and potassium are adulterated in lithium titanate anode material, is necessarily being filled Under discharge-rate, the specific capacity of lithium battery can improve 40%, and have higher cyclical stability.
Brief description of the drawings
Fig. 1 is that lithium titanate is the lithium ion battery that negative material assembles（a′）With addition iron and the lithium titanate anode material of potassium Specific discharge capacity circulation figure of the battery (b ') for expecting to assemble under 0.2C multiplying powers.
Fig. 2 is that lithium titanate is the lithium ion battery that negative material assembles（a′）With addition iron and the lithium titanate anode material of potassium Specific discharge capacity circulation of the battery (b ') for expecting to assemble respectively under 0.5C, 1C, 2C multiplying power is schemed.
Fig. 3 is lithium titanate anode material for lithium ion battery（a）With addition iron and the lithium titanate anode material of potassium（b）Amplification 4 SEM photograph after ten thousand times.
Embodiment
Following embodiments are used to illustrate the present invention.
Embodiment 1
Butyl titanate is chosen as titanium source, lithium acetate is as lithium source, and the potassium ferricyanide is as source of iron, and potassium nitrate is as potassium Source, is Li by the amount ratio that lithium source, titanium source, source of iron and potassium resource press material:Ti:Fe:K=0.85:1:0.0065:0.0195 ratio Weighed respectively.Afterwards, lithium source, source of iron and potassium resource are dissolved in the mixed aqueous solution that three is formed in 40ml deionized waters（It is molten Liquid A）, meanwhile, titanium source is dissolved in 40ml absolute ethyl alcohols and forms ethanol solution（Solution B）, then solution B is added dropwise to solution In A, 1h formation yellow gum solution is stirred on magnetic stirring apparatus, then, obtained yellow gum solution is placed in air blast and is done In 150 DEG C of dry lower 4h in dry case, presoma is obtained, finally grinds presoma in agate mortar, after tabletting, is placed in crucible In in Muffle furnace at a temperature of 800 DEG C, high-temperature calcination 10h, that is, obtain the lithium titanate cathode of lithium ion battery of iron content and potassium Material.
Fig. 1 is the lithium ion battery that lithium titanate anode material assembles（a′）With addition iron and the lithium titanate anode material of potassium Specific discharge capacity circulation figure of the lithium ion battery (b ') assembled under 0.2C multiplying powers.The battery of two kinds of sample assemblies is in 0.2C First discharge specific capacity under multiplying power is respectively 130mAhg-1With 187 mAhg-1, it will be seen that the electric discharge of b ' samples Specific capacity is substantially higher than a ' samples, and specific discharge capacity still may remain in 168 mAhg after the circle of circulation 20-1Left and right, this Illustrate that the suitable iron of doping and potassium help to improve Li4Ti5O12The specific discharge capacity of material.Fig. 2 is a ' and b ' two kinds of samples point Specific discharge capacity circulation figure not under 0.5C, 1C, 2C multiplying power.From the graph, it is apparent that b ' samples are under different multiplying Specific discharge capacity be higher than a ' samples, with the increase of multiplying power, the gap of the specific discharge capacity of two kinds of samples gradually increases, The specific discharge capacity of b ' samples can still maintain 130 mAhg under 2C discharge-rates-1Left and right, and undoped a ' samples Specific discharge capacity only only have 40 mAhg-1Left and right.Thus the doping that we must can tap a blast furnace with potassium can significantly improve battery Specific discharge capacity and cyclical stability under high magnification.
Fig. 3 is lithium titanate anode material（a）With doping iron and the lithium titanate anode material of potassium（b）Amplify the SEM after 40,000 times Photo.A, the average grain diameter estimation of two kinds of samples of b is respectively 650 nm and 350 nm, and therefore, with respect to a samples, b samples have The average grain diameter of smaller.In general, when amount of samples is identical, the particle diameter of sample reduce can increase electrode and electrolyte it Between contact area, therefore, according to Tafel equation it is known that this will greatly reduce electrochemical process polarization, while particle diameter Reduction may be such that lithium ion diffusion path shorten.Therefore b samples show more preferable chemical property.
Embodiment 2
Choosing titanium dioxide, will as potassium resource as source of iron, potassium nitrate as lithium source, iron oxide as titanium source, lithium acetate Lithium source, titanium source, source of iron and potassium resource are Li by the amount ratio of material:Ti:Fe:K=0.55:1:0.03:0.05 ratio is claimed respectively Amount.Afterwards, lithium source, source of iron and potassium resource are dissolved in the mixed aqueous solution of 20ml deionized waters formation three（Solution A）, meanwhile, will Titanium source is dissolved in 20ml absolute ethyl alcohols and forms ethanol solution（Solution B）, then solution B is added dropwise in solution A, in magnetic agitation 0.3h is stirred on device and forms yellow gum solution, then, obtained yellow gum solution is placed in air dry oven in 100 DEG C Lower dry 3h, obtains presoma, finally grinds presoma in agate mortar, after tabletting, is placed in crucible in Muffle furnace At a temperature of 400 DEG C, high-temperature calcination 5h, that is, obtained the lithium titanate anode material for lithium ion battery of iron content and potassium.
Embodiment 3
Titanium dioxide is chosen as titanium source, lithium hydroxide as lithium source, ferric nitrate as source of iron, potassium carbonate as potassium resource, It is Li by the amount ratio that lithium source, titanium source, source of iron and potassium resource press material:Ti:Fe:K=0.95:1:0.15:0.06 ratio carries out respectively Weigh.Afterwards, lithium source, source of iron and potassium resource are dissolved in the mixed aqueous solution that three is formed in 30ml deionized waters（Solution A）, together When, titanium source is dissolved in 20ml absolute ethyl alcohols and forms ethanol solution（Solution B）, then solution B is added dropwise in solution A, in magnetic 0.5h is stirred on power blender and forms yellow gum solution, then, obtained yellow gum solution is placed in air dry oven In 160 DEG C of dry lower 2h, presoma is obtained, finally grinds presoma in agate mortar.After tabletting, it is placed in crucible in horse Not in stove at a temperature of 500 DEG C, high-temperature calcination 4h, that is, obtain the lithium titanate anode material for lithium ion battery of iron content and potassium.
Embodiment 4
Choosing titanium dioxide, will as potassium resource as source of iron, potassium nitrate as lithium source, iron oxide as titanium source, lithium carbonate Lithium source, titanium source, source of iron and potassium resource are Li by the amount ratio of material:Ti:Fe:K=1.5:1:0.2:0.09 ratio is claimed respectively Amount.Afterwards, lithium source, source of iron and potassium resource are dissolved in the mixed aqueous solution that three is formed in 40ml deionized waters（Solution A）, meanwhile, Titanium source is dissolved in 10ml absolute ethyl alcohols and forms ethanol solution（Solution B）, then solution B is added dropwise in solution A, stirred in magnetic force Mix and 1h formation yellow gum solution is stirred on device, then, obtained yellow gum solution is placed in air dry oven in 80 DEG C Lower dry 4h, obtains presoma, finally grinds presoma in agate mortar, after tabletting, is placed in crucible in Muffle furnace At a temperature of 600 DEG C, high-temperature calcination 5h, that is, obtain the lithium titanate anode material for lithium ion battery of iron content and potassium.
Embodiment 5
Butyl titanate is chosen as titanium source, lithium acetate is as lithium source, and the potassium ferricyanide is as source of iron, and potassium nitrate is as potassium Source, is Li by the amount ratio that lithium source, titanium source, source of iron and potassium resource press material:Ti:Fe:K=1.8:1:0.25:0.16 ratio respectively into Row weighs.Afterwards, lithium source, source of iron and potassium resource are dissolved in the mixed aqueous solution of 30ml deionized waters formation three（Solution A）, together When, titanium source is dissolved in 10ml absolute ethyl alcohols and forms ethanol solution（Solution B）, then solution B is added dropwise in solution A, in magnetic 1.5h is stirred on power blender and forms yellow gum solution, then, obtained yellow gum solution is placed in air dry oven Dry 4h, obtains presoma, finally grinds presoma in agate mortar, after tabletting, be placed in crucible in horse at 100 DEG C Not in stove at a temperature of 700 DEG C, high-temperature calcination 4h, that is, obtain the lithium titanate anode material for lithium ion battery of iron content and potassium.
Embodiment 6
Titanium dioxide is chosen as titanium source, lithium carbonate is as lithium source, and iron oxide is as source of iron, a kind of conduct in potassium carbonate Potassium resource, is Li by the amount ratio that lithium source, titanium source, source of iron and potassium resource press material:Ti:Fe:K=1.6:1:0.34:0.2 ratio difference Weighed.Afterwards, lithium source, source of iron and potassium resource are dissolved in the mixed aqueous solution that three is formed in 20ml deionized waters（Solution A）, Meanwhile titanium source is dissolved in 30ml absolute ethyl alcohols and forms ethanol solution（Solution B）, then solution B is added dropwise in solution A, 2h is stirred on magnetic stirring apparatus and forms yellow gum solution, then, obtained yellow gum solution is placed in air dry oven Dry 2h, obtains presoma, finally grinds presoma in agate mortar, after tabletting, be placed in crucible in horse at 180 DEG C Not in stove at a temperature of 600 DEG C, high-temperature calcination 6h, that is, obtain the lithium titanate anode material for lithium ion battery of iron content and potassium.

Claims (5)

1. the preparation method of the lithium titanate anode material for lithium ion battery of a kind of iron content and potassium, it is characterised in that including following step Suddenly：
（1）The preparation of material
It is Li by the amount ratio that lithium source, titanium source, source of iron and potassium resource press material:Ti:Fe：K=(0.3~2.0):1:(0~0.5)：（0~ 0.6）Ratio weighed respectively；
（2）The formation of colloidal solution
Lithium source, source of iron and potassium resource are dissolved in the mixed aqueous solution A that three is formed in deionized water, meanwhile, titanium source is dissolved in anhydrous Ethanol solution B is formed in ethanol, then solution B is added dropwise in solution A, 0.1~2.5h shapes are stirred on magnetic stirring apparatus Yellowly colloidal solution；
（3）Drying and calcining
Obtained yellow gum solution is placed in air dry oven at 40~200 DEG C dry 1~8h, obtains presoma, will Presoma is ground in agate mortar, after tabletting, is placed in crucible in Muffle furnace at a temperature of 400~900 DEG C, and calcining 4~ 15h, obtains the lithium titanate anode material of iron content and potassium.
2. preparation method according to claim 1, it is characterised in that lithium source is lithium carbonate, in lithium acetate, lithium hydroxide It is a kind of.
3. preparation method according to claim 1, it is characterised in that titanium source is one in butyl titanate, titanium dioxide Kind.
4. preparation method according to claim 1, it is characterised in that source of iron is the potassium ferricyanide, in iron oxide, ferric nitrate It is a kind of.
5. preparation method according to claim 1, it is characterised in that potassium resource is one kind in potassium nitrate and potassium carbonate.
CN201610452474.9A 2016-06-22 2016-06-22 A kind of preparation method of the lithium titanate anode material for lithium ion battery of iron content and potassium Expired - Fee Related CN105914357B (en)

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