CN109817938A - A kind of preparation method of iron-based negative electrode material - Google Patents
A kind of preparation method of iron-based negative electrode material Download PDFInfo
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- CN109817938A CN109817938A CN201910113772.9A CN201910113772A CN109817938A CN 109817938 A CN109817938 A CN 109817938A CN 201910113772 A CN201910113772 A CN 201910113772A CN 109817938 A CN109817938 A CN 109817938A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention belongs to technical field of lithium ion, and in particular to a kind of preparation method of iron-based negative electrode material.Using nano iron oxide chemical nickel plating on surface, ferric oxide particles nanosizing can be increased to the contact area of iron oxide, enhance chemical property.Chemical plating is a kind of sufacing easy to operate, can be deposited on iron oxide material surface, and coating is uniform, has good covering property, anticorrosive and wear-resisting property.One layer of preferable substance of electric conductivity is plated on the surface of iron-based negative electrode material by chemical plating, it can be improved the electric conductivity of material, and inhibit volume expansion problem in cyclic process, it repeats 2-3 plating process of progress and avoids plating leakage phenomenon, to further improve the chemical property of negative electrode material, a kind of high performance iron-based negative electrode material is made.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of preparation method of iron-based negative electrode material.
Background technique
Energy density is big, operating voltage is high, self discharge is small, memory-less effect, temperature range are wide because having for lithium ion battery
The advantages that become the most excellent secondary cell of current comprehensive performance.Relative to traditional graphite cathode material (theoretical specific capacity
372mAh/g), Fe2O3(theoretical specific capacity 1005mAh/g) is used as lithium ion battery negative material, has caused people's height
The concern of degree.However, Fe during lithium ion is embedded in and is deviate from2O3Dusting and serious particle aggregation can occur, to lead
Electron-transport and diffusion is caused to reduce, capacity attenuation is too fast, and cycle period is shorter, has severely impacted it as negative electrode material
Further applying in terms of lithium ion battery.
Summary of the invention
The purpose of the present invention is overcoming above-mentioned the shortcomings of the prior art, a kind of preparation side of iron-based negative electrode material is provided
Method, the electric conductivity of material is improved by the surface chemical plating of iron-based negative electrode material, and the volume expansion in cyclic process is inhibited to ask
Topic prepares a kind of high performance iron-based negative electrode material.
To achieve the above object, the invention adopts the following technical scheme:
A kind of preparation method of iron-based negative electrode material, comprising the following steps:
(1) iron-based material is taken, the iron-based material is nano iron oxide powder；It is roughened, sensitization activation；
(2) it prepares plating solution: after main salt solution and enveloping agent solution are mixed, sequentially adding stabilizer and surface-active
Agent is uniformly mixed, and plating solution is made；The main salt is nickel salt；Main salt solution concentration is 10-40g/L in plating solution, and complexing agent concentration is
0.03-006mol/L, stabilizer concentration are (1~3) × 10-6Mol/L, surfactant concentration are (0.5~1.5) × 10- 6mol/L；
(3) iron-based material is added in plating solution after activating, and adjusting bath pH value is 12-13, is slowly added to reducing agent, carries out
Chemical plating, wherein the chemical plating temperature is 65-70 DEG C, plating time 70-120min；
(4) it is dried after cleaning iron-based material after chemical plating with deionized water, iron-based lithium ion battery negative material is made.
In the step (1), the preparation process of nano iron oxide powder are as follows: a certain amount of Iron trichloride hexahydrate is taken to be dissolved in
In ionized water, sodium hydroxide solution, regulation system pH value to more than 10 is added dropwise.Products therefrom is transferred in autoclave,
200 DEG C of hydro-thermal reaction 10h.It is filtered by vacuum after cooling, red product is obtained by filtration, after product is washed with deionized, be put into
The dry 12h of 60 DEG C of thermostatic drying chambers.It is placed in clean crucible after dry gained sample is taken out, is forged for 300 DEG C in Muffle furnace
Burn 2h.
In the step (1), the coarsening process of iron-based material are as follows: with the nitric acid solution of volume fraction 10%, ultrasound is stirred
Middle roughening acidification 5min is mixed, and is cleaned with distilled water to neutrality.
In the step (1), the sensitization of iron-based material activation using the sensitization activation method of fractional steps, the configuration of sensitizing solution by
10g sensitizer+40ml concentrated hydrochloric acid+1000ml distilled water.A certain amount of powder by oil removing is weighed in quantitative sensitizing solution,
Under the ultrasonic agitation of 150W, it is sensitized 3~5min, is taken out, no chloride ion is washed to distillation and exists.The configuration of activating solution by
3.5g silver nitrate+7g/LNaOH solution+100ml/L ammonium hydroxide.It measures in the powder after sensitization is added in a certain amount of activating solution,
Under the ultrasonic agitation of 150W, 10~15min is activated.
In the step (2), nickel salt is specially one of nickel nitrate, nickel sulfate or nickel chloride.
In the step (2), complexing agent is one of ethylenediamine, sodium citrate or disodium ethylene diamine tetraacetate, surely
Determining agent is one of thiocarbamide, urea or ammonium sulfide, and surfactant is lauryl sodium sulfate, dodecyl sodium sulfate or ten
One of dialkyl benzene sulfonic acids sodium.
In the step (3), reducing agent is hydrazine hydrate, and additive amount is the 10-150ml/L of plating solution.
In the step (4), chemical plating number is 2~3 times, to avoid plating leakage situation.
When the iron-based negative electrode material of above-mentioned preparation is used as negative electrode of lithium ion battery, current density 100mA/g, by 100
After circulation, specific capacity is stablized in 650-800mAh/g, and coulombic efficiency reaches 96-98%.
In the present invention, ferric oxide particles nanosizing can be increased to the contact area of iron oxide, enhance chemical property.Change
Learning plating is a kind of sufacing easy to operate, can be deposited on iron oxide material surface, and coating is uniform, is had good
Covering property, anticorrosive and wear-resisting property.Therefore, by chemical plating the surface of iron-based negative electrode material plate one layer of electric conductivity compared with
Good substance, can be improved the electric conductivity of material, and inhibit the volume expansion problem in cyclic process, repeat progress 2-3 times
Plating process avoids plating leakage phenomenon, to further improve the chemical property of negative electrode material.
Beneficial effects of the present invention:
The present invention uses nano iron oxide chemical nickel plating on surface or even secondary chemical plating, so that the electric conductivity of material is improved,
And the volume expansion problem in iron-based negative electrode material cyclic process is buffered, improve chemical property.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.
Embodiment 1
(1) it takes a certain amount of Iron trichloride hexahydrate to be dissolved in deionized water, sodium hydroxide solution is added dropwise, regulation system pH value is extremely
Greater than 10.Products therefrom is transferred in autoclave, 200 DEG C of hydro-thermal reaction 10h.It is filtered by vacuum, is obtained by filtration after cooling
Red product after product is washed with deionized, is put into the dry 12h of 60 DEG C of thermostatic drying chambers.Dry gained sample is taken out
It is placed in clean crucible afterwards, 300 DEG C of calcining 2h in Muffle furnace.Obtain nano iron oxide powder；(2) by Nano-sized Ferric Oxide Powder
It is put into nitric acid coarsening solution, is stirred at room temperature, carried out after being cleaned by deionized water to neutrality using the sensitization activation method of fractional steps
Sensitization activation；(3) after mixing nickel sulfate solution and 0.05mol/L ethylenediamine solution, 2 × 10 are sequentially added-6Mol/L thiocarbamide
With 1 × 10-6Mol/L lauryl sodium sulfate, wherein main salt concentration is 20g/L；(4) step is added in the product for obtaining step (2)
Suddenly in the plating solution that (3) are prepared, pH value is adjusted to 12, hydrazine hydrate solution chemical plating 60min at 70 DEG C is slowly added to, wherein being hydrated
Hydrazine dosage is 50ml/L；(5) it is dried after being cleaned with deionized water；(6) repeat secondary chemical plating, iron-based cathode material is made
Material.The negative electrode material is used as negative electrode of lithium ion battery, and in the case where current density is 100mA/g after 100 circulations, specific capacity is stablized
In 655mAh/g, coulombic efficiency 96.5%.
Embodiment 2
(1) it takes a certain amount of Iron trichloride hexahydrate to be dissolved in deionized water, sodium hydroxide solution is added dropwise, regulation system pH value is extremely
Greater than 10.Products therefrom is transferred in autoclave, 200 DEG C of hydro-thermal reaction 10h.It is filtered by vacuum, is obtained by filtration after cooling
Red product after product is washed with deionized, is put into the dry 12h of 60 DEG C of thermostatic drying chambers.Dry gained sample is taken out
It is placed in clean crucible afterwards, 300 DEG C of calcining 2h in Muffle furnace.Obtain nano iron oxide powder；(2) by Nano-sized Ferric Oxide Powder
It is put into nitric acid coarsening solution, is stirred at room temperature, carried out after being cleaned by deionized water to neutrality using the sensitization activation method of fractional steps
Sensitization activation；(3) after mixing nickel sulfate solution and 0.05mol/L ethylenediamine solution, 2 × 10 are sequentially added-6Mol/L thiocarbamide
With 1 × 10-6Mol/L lauryl sodium sulfate, wherein main salt concentration is 30g/L；(4) step is added in the product for obtaining step (2)
Suddenly in the plating solution that (3) are prepared, pH value is adjusted to 13, hydrazine hydrate solution chemical plating 60min at 65 DEG C is slowly added to, wherein being hydrated
Hydrazine dosage is 50ml/L；(5) it is dried after being cleaned with deionized water；(6) repeat secondary chemical plating, iron-based cathode material is made
Material.The negative electrode material is used as negative electrode of lithium ion battery, and in the case where current density is 100mA/g after 100 circulations, specific capacity is stablized
In 780mAh/g, coulombic efficiency 97.55%.
Claims (9)
1. a kind of preparation method of iron-based negative electrode material, which comprises the following steps:
(1) iron-based material is taken, the iron-based material is nano iron oxide powder；It is roughened, sensitization activation；
(2) it prepares plating solution: after main salt solution and enveloping agent solution are mixed, sequentially adding stabilizer and surfactant, mix
It closes uniformly, plating solution is made；The main salt is nickel salt；Main salt solution concentration is 10-40g/L, complexing agent concentration 0.03- in plating solution
006mol/L, stabilizer concentration are (1~3) × 10-6Mol/L, surfactant concentration are (0.5~1.5) × 10-6mol/L；
(3) iron-based material is added in plating solution after activating, and adjusting bath pH value is 12-13, is slowly added to reducing agent, carries out chemistry
Plating, wherein the chemical plating temperature is 65-70 DEG C, plating time 70-120min；
(4) it is dried after cleaning iron-based material after chemical plating with deionized water, iron-based lithium ion battery negative material is made.
2. a kind of preparation method of iron-based negative electrode material according to claim 1, which is characterized in that the step (2)
In, nickel salt is one of nickel nitrate, nickel sulfate or nickel chloride.
3. a kind of preparation method of iron-based negative electrode material according to claim 1 or 2, which is characterized in that the step
(1) in, the preparation process of nano iron oxide powder are as follows: take a certain amount of Iron trichloride hexahydrate to be dissolved in deionized water, hydrogen-oxygen is added dropwise
Change sodium solution, regulation system pH value to more than 10；Products therefrom is transferred in autoclave, 200 DEG C of hydro-thermal reaction 10h；
It is filtered by vacuum after cooling, red product is obtained by filtration, after product is washed with deionized, it is dry to be put into 60 DEG C of thermostatic drying chambers
12h；It is placed in clean crucible after dry gained sample is taken out, 300 DEG C of calcining 2h in Muffle furnace.
4. a kind of preparation method of iron-based negative electrode material according to claim 1 or 2, which is characterized in that the step
(1) in, the coarsening process of iron-based material are as follows: with the nitric acid solution of volume fraction 10%, be roughened acidification in ultrasonic agitation
5min, and cleaned with distilled water to neutrality.
5. a kind of preparation method of iron-based negative electrode material according to claim 1 or 2, which is characterized in that the step
(1) in, the sensitization activation of iron-based material is using the sensitization activation method of fractional steps, and the configuration of sensitizing solution is by 10g sensitizer+40ml concentrated hydrochloric acid
+ 1000ml distilled water；A certain amount of powder by oil removing is weighed in quantitative sensitizing solution, under the ultrasonic agitation of 150W,
It is sensitized 3~5min, is taken out, no chloride ion is washed to distillation and exists；The configuration of activating solution is by 3.5g silver nitrate+7g/LNaOH
Solution+100ml/L ammonium hydroxide；It measures in the powder after sensitization is added in a certain amount of activating solution, under the ultrasonic agitation of 150W, activation
10~15min.
6. a kind of preparation method of iron-based negative electrode material according to claim 1 or 2, which is characterized in that the step
(2) in, complexing agent is one of ethylenediamine, sodium citrate or disodium ethylene diamine tetraacetate, and stabilizer is thiocarbamide, urea or sulphur
Change one of ammonium, surfactant is in lauryl sodium sulfate, dodecyl sodium sulfate or neopelex
It is a kind of.
7. a kind of preparation method of iron-based negative electrode material according to claim 1 or 2, which is characterized in that the step
(3) in, reducing agent is hydrazine hydrate, and additive amount is the 10-150ml/L of plating solution.
8. a kind of preparation method of iron-based negative electrode material according to claim 1 or 2, which is characterized in that the step
(4) in, chemical plating number is 2~3 times, to avoid plating leakage situation.
9. the application of the iron-based negative electrode material of claim 1~8 any the method preparation, which is characterized in that preparation it is iron-based
When negative electrode material is used as negative electrode of lithium ion battery, current density 100mA/g, after 100 circulations, specific capacity is stablized in 650-
800mAh/g, coulombic efficiency reach 96-98%.
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