CN103413942A - Preparation method for low-cost high-electrical conductivity lithium ion battery positive pole material - Google Patents
Preparation method for low-cost high-electrical conductivity lithium ion battery positive pole material Download PDFInfo
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- CN103413942A CN103413942A CN2013103248165A CN201310324816A CN103413942A CN 103413942 A CN103413942 A CN 103413942A CN 2013103248165 A CN2013103248165 A CN 2013103248165A CN 201310324816 A CN201310324816 A CN 201310324816A CN 103413942 A CN103413942 A CN 103413942A
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Abstract
The invention relates to a preparation method for a low-cost high-electrical conductivity lithium ion battery positive pole material. The method is characterized by comprising the following steps: dissolving soluble phosphate and Fe salt in deionized water according to stoichiometric ratio, so as to prepare a 0.1-3 mol/L solution A; dripping a 1-7 percent cupric sulfate solution in a 1-10 percent sodium hydroxide solution to obtain a transparent fehling reagent solution; slowly dripping the solution A into the fehling reagent solution to form a solution B; slowly dripping 20-40 percent formalin into the solution B, performing magnetic agitating at the temperature of 70-90 DEG C to form a powdered precursor for grinding and reserving; putting the precursor into a pipe furnace filled with inert or reducing gas for pre-processing sintering so as to obtain the pre-processing powder; allowing the pre-processing powder in the pipe furnace filled with the inert or reducing gas to be subjected to sintering again, thereby obtaining a copper clad ferrous phosphate lithium material. The prepared material is high in electric conductivity, and multiplying power performance and circulating stability of the ferrous phosphate lithium material can be improved very conveniently.
Description
Technical field
The present invention relates to a kind of low-cost high conductivity method for preparing anode material of lithium-ion battery, specifically, relate to a kind of preparation method with copper clad lithium iron phosphate cathode material of low-cost high conductivity, belong to the anode material for lithium-ion batteries technical field.
Background technology
Lithium rechargeable battery, since commercialization, has been used widely in many fields such as portable electric appts, LiCoO
2Because the advantages such as voltage height and stable electrochemical property occupy critical role on market.But the Co resource lacks relatively, expensive, limited its application.
In recent years, the positive electrode of a class with polyanion type structure caused people's extensive concern.Wherein, LiFePO 4 (LiFePO
4) be the positive electrode with polyanion type structure that people know the earliest, because it has stable structure, higher specific capacity, cheap price and the advantage such as environmentally friendly causes showing great attention to of people, be considered to current optimal power lithium-ion battery positive electrode.At LiFePO
4In material structure, larger phosphate anion has substituted the oxonium ion in traditional metal oxide type positive electrode, has improved on the one hand LiFePO
4The structural stability of material, and then improved the cyclical stability of material.But, but increased the distance between the metallic iron ion on the one hand in addition, reduced LiFePO
4Electronic conductivity.
At present, for LiFePO
4The problem that conductivity is lower, the researcher is mainly by carrying out material with carbon-coated surface and preparing composite material and solve to it.Patent CN102088079, CN102013478 etc. disclose a kind of preparation method of carbon cladded ferrous lithium phosphate, although carbon coats the conductivity that can improve to a certain extent LiFePO 4, but also reduced the tap density of this material simultaneously, and then had influence on its energy density; Patent CN101891179 and CN102034980 disclose a kind of method for preparing lithium ferrous phosphate composite material with the metal simple-substance aluminium powder, but this procedure is comparatively complicated, and conductivity improves limited.
Given this, this patent will utilize formaldehyde bronze mirror reaction principle by simple preparation technology, prepare the copper clad lithium iron phosphate cathode material.Patent searching, also do not have to find to react by bronze mirror the Patents that former lithium prepares the copper clad ferrousphosphate lithium material.
Summary of the invention
The purpose of this invention is to provide a kind of low-cost high conductivity method for preparing anode material of lithium-ion battery, its material electric conductivity prepared is higher, is very beneficial for improving high rate performance and the cyclical stability of ferrousphosphate lithium material.
Technical scheme of the present invention is achieved in that a kind of low-cost high conductivity method for preparing anode material of lithium-ion battery, it is characterized in that concrete preparation process is as follows:
A) soluble phosphate, Fe salt are dissolved in deionized water according to stoichiometric proportion, being mixed with concentration is the A solution of 0.1 ~ 3mol/L;
B) by concentration, be 1 ~ 7% copper-bath to splash into concentration be, in 1 ~ 10% sodium hydroxide solution, to have gradually precipitation to generate, more dropwise drip sodium potassium tartrate tetrahydrate until precipitation disappears, obtain transparent fehling reagent solution;
C) A solution is slowly splashed in fehling reagent, regulating PH is 9 ~ 10, forms B solution;
D) by concentration, be that 20 ~ 40% formalin slowly splashes in B solution, and carry out magnetic agitation at the temperature of 70 ~ 90 ℃, until form Powdered precursor, grind standby;
E) precursor is put into to the tube furnace that is connected with inertia or reducibility gas protection and carried out the preliminary treatment sintering, obtain the preliminary treatment powder;
F) above-mentioned preliminary treatment powder is carried out to sintering again in the tube furnace that is connected with inertia or reducibility gas protection, control heating rate, sintering temperature, sintering time, cooling method, can obtain the copper clad ferrousphosphate lithium material.
In described step a), phosphate is lithium dihydrogen phosphate, lithium phosphate; Described Fe salt comprises ferrous nitrate, ferrous acetate and ferrous oxalate.
In described step a) in Fe salt and step b) in copper-bath the mol ratio of copper be Fe:Cu=(10 ~ 100): 1.
In described step d), the concentration range of formalin is 20 ~ 40%, in formaldehyde and step b) in copper-bath the molar ratio range of copper be (1 ~ 1.5): 1.
In described step e), inert gas comprises the mist of argon gas, nitrogen or two kinds; Reducibility gas comprises hydrogen and argon gas blender, hydrogen and nitrogen mixture, and described pretreatment temperature scope is 300 ~ 450 ℃, and pretreatment time is 3 ~ 10 hours.
In described step f), inert gas comprises argon gas, nitrogen; Reducibility gas comprises hydrogen and argon gas gaseous mixture, hydrogen and nitrogen mixture, and described heating rate is 10 ~ 20 ℃/min, and sintering temperature is 600 ~ 900 ℃, and sintering time is 4 ~ 15 hours; Described cooling method have with stove cool, Quenching in liquid nitrogen.
Good effect of the present invention is:
1) utilize the bronze mirror reaction principle of formaldehyde, prepare and have the ferrousphosphate lithium material that surface copper coats, this material electric conductivity is higher, and copper exists with metallic forms, and is evenly distributed;
2) formaldehyde had both played the effect of carbon source in course of reaction, was also simultaneously the important source material of bronze mirror reaction;
3) adopt this method synthetic LiFePO 4 good rate capability, cycle performance excellence.
The accompanying drawing explanation
Fig. 1 be in example 1 of the present invention material charge and discharge resolution chart.
Fig. 2 is the cycle performance resolution chart of material in example 1 of the present invention.
Fig. 3 is 0 ~ 60 ° of XRD resolution chart of material in example 2 of the present invention.
Embodiment
In following specific embodiment is described, provided a large amount of concrete details and the understanding more deep to the present invention just is provided.Yet, it will be apparent to one skilled in the art that the present invention can be implemented without one or more these details.In other example, for fear of with the present invention, obscuring, for technical characterictics more well known in the art for being described.
Embodiment 1
By lithium dihydrogen phosphate and ferrous nitrate in molar ratio the ratio of Li:Fe=1:1 be dissolved in appropriate deionized water, be mixed with the solution A that concentration is 3mol/L; The copper sulphate of use 1% and 1% NaOH configuration fehling reagent; The ratio of A solution according to Fe:Cu=10:1 slowly splashed in fehling reagent, then by ammoniacal liquor, the pH value of solution is adjusted to 9; It is 9 solution that the concentration formalin that is 20% is slowly splashed into to above-mentioned pH value, under 70 ℃, carries out magnetic agitation, forms precursor; After precursor is simply ground, put into the tube furnace that is connected with argon shield and carry out sintering, sintering temperature is 300 ℃, and sintering time is 3 hours, obtains the preliminary treatment powder; The preliminary treatment powder is carried out to sintering again in the tube furnace that is connected with argon gas and hydrogen hybrid protection gas; sintering temperature is 900 ℃ of (10 ℃ of heating rates/min); sintering time is 4 hours, adopts and lowers the temperature with the cooling mode of stove, can obtain 3.3wt% copper clad ferrousphosphate lithium material.Fig. 1 be this material in 2.7 ~ 4.2V interval, the charging and discharging curve of battery under the 0.1C multiplying power, negative pole adopt lithium metal.The initial charge capacity of material is 152mAhg
-1, discharge capacity is 149.4mAhg
-1, efficiency for charge-discharge is higher.Fig. 2 is the cycle performance of this material under each discharge-rate, and the cycle performance of this material is better as seen.
Embodiment 2
By lithium phosphate and ferrous oxalate in molar ratio the ratio of Li:Fe=1:1 be dissolved in appropriate deionized water, be mixed with the solution A that concentration is 0.1mol/L; The copper sulphate of use 7% and 10% NaOH configuration fehling reagent; The ratio of A solution according to Fe:Cu=100:1 slowly splashed in fehling reagent, then by ammoniacal liquor, the pH value of solution is adjusted to 10; It is 10 solution that the concentration formalin that is 40% is slowly splashed into to above-mentioned pH value, under 90 ℃, carries out magnetic agitation, forms precursor; After precursor is simply ground, put into the tube furnace that is connected with nitrogen protection and carry out sintering, sintering temperature is 450 ℃, and sintering time is 10 hours, obtains the preliminary treatment powder; The preliminary treatment powder is carried out to sintering again in the tube furnace that is connected with nitrogen and hydrogen hybrid protection gas; sintering temperature is 600 ℃ of (20 ℃ of heating rates/min); sintering time is 15 hours, adopts the cooling mode of Quenching in liquid nitrogen to lower the temperature, and can obtain 0.16wt% copper clad ferrousphosphate lithium material.Fig. 3 is the XRD collection of illustrative plates of material in 10 ~ 60 ° of scopes, and as can be seen from the figure material is consistent with the XRD collection of illustrative plates of pure phase ferrousphosphate lithium material, and the reason of not seeing metal Cu diffraction maximum is because the content of metal Cu is less.
Embodiment 3
By lithium dihydrogen phosphate and ferrous acetate in molar ratio the ratio of Li:Fe=1:1 be dissolved in appropriate deionized water, be mixed with the solution A that concentration is 1mol/L; The copper sulphate of use 5% and 10% NaOH configuration fehling reagent; The ratio of A solution according to Fe:Cu=50:1 slowly splashed in fehling reagent, then by ammoniacal liquor, the pH value of solution is adjusted to 9; It is 9 solution that the concentration formalin that is 35% is slowly splashed into to above-mentioned pH value, under 80 ℃, carries out magnetic agitation, forms precursor; After precursor is simply ground, put into the tube furnace that is connected with nitrogen protection and carry out sintering, sintering temperature is 400 ℃, and sintering time is 5 hours, obtains the preliminary treatment powder; The preliminary treatment powder is carried out to sintering again in the tube furnace that is connected with nitrogen and hydrogen hybrid protection gas; sintering temperature is 850 ℃ of (15 ℃ of heating rates/min); sintering time is 8 hours, adopts the cooling mode of Quenching in liquid nitrogen to lower the temperature, and can obtain 0.81wt% copper clad ferrousphosphate lithium material.
Claims (6)
1. low-cost high conductivity method for preparing anode material of lithium-ion battery is characterized in that concrete preparation process is as follows:
A) soluble phosphate, Fe salt are dissolved in appropriate deionized water according to stoichiometric proportion, are mixed with the A solution of debita spissitudo;
B) by concentration, be 1 ~ 7% copper-bath to splash into concentration be, in 1 ~ 10% sodium hydroxide solution, to have gradually precipitation to generate, more dropwise drip sodium potassium tartrate tetrahydrate until precipitation disappears, obtain transparent fehling reagent solution;
C) A solution is slowly splashed in fehling reagent, regulating pH value is 9 ~ 10, forms B solution;
D) by concentration, be that 20 ~ 40% formalin slowly splashes in B solution, and carry out magnetic agitation at the temperature of 70 ~ 90 ℃, until form Powdered precursor, grind standby;
E) precursor is put into to the tube furnace that is connected with inertia or reducibility gas protection and carried out the preliminary treatment sintering, obtain the preliminary treatment powder;
F) above-mentioned preliminary treatment powder is carried out to sintering again in the tube furnace that is connected with inertia or reducibility gas protection, control heating rate, sintering temperature, sintering time, cooling method, can obtain the copper clad ferrousphosphate lithium material.
2. a kind of low-cost high conductivity method for preparing anode material of lithium-ion battery according to claim 1, is characterized in that the phosphate in described step a) is lithium dihydrogen phosphate, lithium phosphate; Described Fe salt comprises ferrous nitrate, ferrous acetate and ferrous oxalate; Described A solution concentration is 0.1 ~ 3mol/L.
3. a kind of low-cost high conductivity method for preparing anode material of lithium-ion battery according to claim 1, is characterized in that in described step a) in Fe salt and step b) in copper-bath that the mol ratio of copper is Fe:Cu=(10 ~ 100): 1.
4. a kind of low-cost high conductivity method for preparing anode material of lithium-ion battery according to claim 1, the concentration range that it is characterized in that formalin in described step d) is 20 ~ 40%, in formaldehyde and step b) in copper-bath the molar ratio range of copper be (1 ~ 1.5): 1.
5. a kind of low-cost high conductivity method for preparing anode material of lithium-ion battery according to claim 1, is characterized in that in described step e), inert gas comprises argon gas, nitrogen; Reducibility gas comprises hydrogen and argon gas gaseous mixture, hydrogen and nitrogen mixture, and described pretreatment temperature scope is 300 ~ 450 ℃, and pretreatment time is 3 ~ 10 hours.
6. a kind of low-cost high conductivity method for preparing anode material of lithium-ion battery according to claim 1, is characterized in that inert gas in described step f) comprises the mist of argon gas, nitrogen or two kinds; Reducibility gas comprises hydrogen and argon gas blender, hydrogen and nitrogen mixture, and described heating rate is 10 ~ 20 ℃/min, and sintering temperature is 600 ~ 900 ℃, and sintering time is 4 ~ 15 hours; Described cooling method have with stove cool, Quenching in liquid nitrogen.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114368736A (en) * | 2022-01-28 | 2022-04-19 | 中南大学 | Preparation method of olivine type sodium iron phosphate cathode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101621122A (en) * | 2009-08-07 | 2010-01-06 | 珠海市鹏辉电池有限公司 | Preparation method of lithium iron phosphate compound material |
| CN102664261A (en) * | 2012-05-16 | 2012-09-12 | 中国第一汽车股份有限公司 | Method for preparing high-conductivity lithium ion battery cathode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101621122A (en) * | 2009-08-07 | 2010-01-06 | 珠海市鹏辉电池有限公司 | Preparation method of lithium iron phosphate compound material |
| CN102664261A (en) * | 2012-05-16 | 2012-09-12 | 中国第一汽车股份有限公司 | Method for preparing high-conductivity lithium ion battery cathode material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114368736A (en) * | 2022-01-28 | 2022-04-19 | 中南大学 | Preparation method of olivine type sodium iron phosphate cathode material |
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