CN103413942B - A kind of method for preparing anode material of lithium-ion battery - Google Patents
A kind of method for preparing anode material of lithium-ion battery Download PDFInfo
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- CN103413942B CN103413942B CN201310324816.5A CN201310324816A CN103413942B CN 103413942 B CN103413942 B CN 103413942B CN 201310324816 A CN201310324816 A CN 201310324816A CN 103413942 B CN103413942 B CN 103413942B
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Abstract
The present invention relates to a kind of preparation method for low-cost high-electrical conductivity lithium ion battery positive pole material, it is characterized in that concrete preparation process is as follows: soluble phosphate, Fe salt are dissolved in deionized water according to stoichiometric proportion, are mixed with the solution A of 0.1 ~ 3mol/L; By in the sodium hydroxide solution of the copper-bath of 1 ~ 7% instillation 1 ~ 10%, obtain transparent fehling reagent solution; Solution A is slowly instilled in fehling reagent, forms B solution; The formalin of 20 ~ 40% is slowly instilled in B solution, and carry out magnetic agitation at the temperature of 70 ~ 90 DEG C, until form Powdered precursor, grind for subsequent use; Precursor is put into the tube furnace being connected with inertia or reducibility gas protection and carry out preliminary treatment sintering, obtain preliminary treatment powder; Above-mentioned preliminary treatment powder is again sintered in the tube furnace being connected with inertia or reducibility gas protection, copper clad ferrousphosphate lithium material can be obtained.Its material electric conductivity prepared is higher, is very beneficial for the high rate performance and the cyclical stability that improve ferrousphosphate lithium material.
Description
Technical field
The present invention relates to a kind of method for preparing anode material of lithium-ion battery, specifically, relate to a kind of preparation method with the copper clad lithium iron phosphate cathode material of low cost high conductivity, belong to 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 commercially occupy critical role.But Co resource lacks relatively, expensive, limit its application.
In recent years, the positive electrode that a class has a polyanionic structure causes people's extensive concern.Wherein, LiFePO 4 (LiFePO
4) be the positive electrode with polyanionic structure that people know the earliest, cause showing great attention to of people because it has stable structure, higher specific capacity, cheap price and the advantage such as environmentally friendly, be considered to current optimal power lithium-ion battery positive electrode.At LiFePO
4in material structure, larger phosphate anion instead of the oxonium ion in INVENTIONConventional metal-oxide type positive electrode, improves LiFePO on the one hand
4the structural stability of material, and then the cyclical stability that improve material.But, but add the distance between metallic iron ion in addition on the one hand, reduce LiFePO
4electronic conductivity.
At present, for LiFePO
4the problem that conductivity is lower, researcher solves mainly through carrying out material with carbon-coated surface to it and preparing composite material.Patent CN102088079, CN102013478 etc. disclose a kind of preparation method of carbon cladded ferrous lithium phosphate, although the coated conductivity that can improve LiFePO 4 to a certain extent of carbon, but also reduce the tap density of this material simultaneously, and then have influence on its energy density; Patent CN101891179 and CN102034980 discloses a kind of metal simple-substance aluminium powder to prepare the method for lithium ferrous phosphate composite material, but this procedure is comparatively complicated, and conductivity improves limited.
Given this, this patent by simple preparation technology, will utilize formaldehyde bronze mirror reaction principle, prepares copper clad lithium iron phosphate cathode material.Patent searching, does not also find to react by bronze mirror the Patents that former lithium prepares copper clad ferrousphosphate lithium material.
Summary of the invention
The object of this invention is to provide a kind of method for preparing anode material of lithium-ion battery, its material electric conductivity prepared is higher, is very beneficial for the high rate performance and the cyclical stability that improve ferrousphosphate lithium material.
Technical scheme of the present invention is achieved in that a kind of 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, are mixed with the solution A that concentration is 0.1 ~ 3mol/L;
B) by concentration be 1 ~ 7% copper-bath instillation concentration be in the sodium hydroxide solution of 1 ~ 10%, have gradually precipitation generate, more dropwise drip sodium potassium tartrate tetrahydrate until precipitation disappear, obtain transparent fehling reagent solution;
C) solution A is slowly instilled in fehling reagent, regulate PH to be 9 ~ 10, form B solution;
D) by concentration be 20 ~ 40% formalin slowly instill in B solution, and carry out magnetic agitation at the temperature of 70 ~ 90 DEG C, until form Powdered precursor, grind for subsequent use;
E) precursor is put into the tube furnace being connected with inertia or reducibility gas protection and carry out preliminary treatment sintering, obtain preliminary treatment powder;
F) above-mentioned preliminary treatment powder is again sintered in the tube furnace being connected with inertia or reducibility gas protection, control heating rate, sintering temperature, sintering time, cooling method, copper clad ferrousphosphate lithium material can be obtained.
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 is Fe:Cu=(10 ~ 100): 1.
In described step d), the concentration range of formalin is 20 ~ 40%, and in formaldehyde and step b), in copper-bath, the molar ratio range of copper is (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 DEG C, 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 DEG C/min, and sintering temperature is 600 ~ 900 DEG C, and sintering time is 4 ~ 15 hours; Described cooling method have cool with stove, Quenching in liquid nitrogen.
Good effect of the present invention is:
1) utilize the bronze mirror reaction principle of formaldehyde, prepare and have the coated ferrousphosphate lithium material of surface copper, 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 the important source material of bronze mirror reaction simultaneously;
3) adopt the LiFePO 4 good rate capability of this method synthesis, cycle performance excellent.
Accompanying drawing explanation
Fig. 1 is the charge and discharge resolution chart of material in example 1 of the present invention.
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 describes, give a large amount of concrete details and the understanding more deep to the present invention is just provided.But, it will be apparent to one skilled in the art that the present invention can be implemented without the need to these details one or more.In other example, in order to avoid obscuring with the present invention, for technical characteristics more well known in the art for being described.
embodiment 1
The ratio of lithium dihydrogen phosphate and ferrous nitrate Li:Fe=1:1 is in molar ratio dissolved in appropriate deionized water, is mixed with the solution A that concentration is 3mol/L; Use the copper sulphate of 1% and the NaOH configuration fehling reagent of 1%; The ratio of solution A according to Fe:Cu=10:1 is slowly instilled in fehling reagent, then by ammoniacal liquor, the pH value of solution is adjusted to 9; By concentration be 20% formalin slowly instill the solution that above-mentioned pH value is 9, at 70 DEG C, carry out magnetic agitation, formed precursor; After simply being ground by precursor, put into the tube furnace being connected with argon shield and sinter, sintering temperature is 300 DEG C, and sintering time is 3 hours, obtains preliminary treatment powder; Preliminary treatment powder is sintered in the tube furnace being connected with argon gas and hydrogen hybrid protection gas again; sintering temperature is 900 DEG C (heating rate 10 DEG C/min); sintering time is 4 hours, adopts the mode with stove cooling to lower the temperature, can obtain 3.3wt% copper clad ferrousphosphate lithium material.Fig. 1 is that this material is interval at 2.7 ~ 4.2V, and the charging and discharging curve of battery under 0.1C multiplying power, negative pole adopts 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
The ratio of lithium phosphate and ferrous oxalate Li:Fe=1:1 is in molar ratio dissolved in appropriate deionized water, is mixed with the solution A that concentration is 0.1mol/L; Use the copper sulphate of 7% and the NaOH configuration fehling reagent of 10%; The ratio of solution A according to Fe:Cu=100:1 is slowly instilled in fehling reagent, then by ammoniacal liquor, the pH value of solution is adjusted to 10; By concentration be 40% formalin slowly instill the solution that above-mentioned pH value is 10, at 90 DEG C, carry out magnetic agitation, formed precursor; After simply being ground by precursor, put into the tube furnace being connected with nitrogen protection and sinter, sintering temperature is 450 DEG C, and sintering time is 10 hours, obtains preliminary treatment powder; Preliminary treatment powder is sintered in the tube furnace being connected with nitrogen and hydrogen hybrid protection gas again; sintering temperature is 600 DEG C (heating rate 20 DEG C/min); sintering time is 15 hours, adopts the mode of Quenching in liquid nitrogen cooling to lower the temperature, can obtain 0.16wt% copper clad ferrousphosphate lithium material.Fig. 3 is the XRD collection of illustrative plates of material within the scope of 10 ~ 60 °, and as can be seen from the figure material is consistent with the XRD collection of illustrative plates of pure phase ferrousphosphate lithium material, does not see that the reason of Ni metal diffraction maximum is because the content of Ni metal is less.
embodiment 3
The ratio of lithium dihydrogen phosphate and ferrous acetate Li:Fe=1:1 is in molar ratio dissolved in appropriate deionized water, is mixed with the solution A that concentration is 1mol/L; Use the copper sulphate of 5% and the NaOH configuration fehling reagent of 10%; The ratio of solution A according to Fe:Cu=50:1 is slowly instilled in fehling reagent, then by ammoniacal liquor, the pH value of solution is adjusted to 9; By concentration be 35% formalin slowly instill the solution that above-mentioned pH value is 9, at 80 DEG C, carry out magnetic agitation, formed precursor; After simply being ground by precursor, put into the tube furnace being connected with nitrogen protection and sinter, sintering temperature is 400 DEG C, and sintering time is 5 hours, obtains preliminary treatment powder; Preliminary treatment powder is sintered in the tube furnace being connected with nitrogen and hydrogen hybrid protection gas again; sintering temperature is 850 DEG C (heating rate 15 DEG C/min); sintering time is 8 hours, adopts the mode of Quenching in liquid nitrogen cooling to lower the temperature, can obtain 0.81wt% copper clad ferrousphosphate lithium material.
Claims (6)
1. a method for preparing anode material of lithium-ion battery, is characterized in that concrete preparation process is as follows:
A) by being dissolved in appropriate deionized water containing the soluble phosphate of elemental lithium, Fe salt according to stoichiometric proportion, the solution A of debita spissitudo is mixed with;
B) by concentration be 1 ~ 7% copper-bath instillation concentration be in the sodium hydroxide solution of 1 ~ 10%, have gradually precipitation generate, more dropwise drip sodium potassium tartrate tetrahydrate until precipitation disappear, obtain transparent fehling reagent solution;
C) solution A is slowly instilled in fehling reagent, regulate pH value to be 9 ~ 10, form B solution;
D) by concentration be 20 ~ 40% formalin slowly instill in B solution, and carry out magnetic agitation at the temperature of 70 ~ 90 DEG C, until form Powdered precursor, grind for subsequent use;
E) precursor is put into the tube furnace being connected with inertia or reducibility gas protection and carry out preliminary treatment sintering, obtain preliminary treatment powder;
F) above-mentioned preliminary treatment powder is again sintered in the tube furnace being connected with inertia or reducibility gas protection, control heating rate, sintering temperature, sintering time, cooling method, copper clad ferrousphosphate lithium material can be obtained.
2. a kind of 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 solution A concentration is 0.1 ~ 3mol/L.
3. a kind of method for preparing anode material of lithium-ion battery according to claim 1, to is characterized in that in described step a) that in Fe salt and step b), in copper-bath, the mol ratio of copper is Fe:Cu=(10 ~ 100): 1.
4. a kind of method for preparing anode material of lithium-ion battery according to claim 1, is characterized in that the concentration range of formalin in described step d) is 20 ~ 40%, and in formaldehyde and step b), in copper-bath, the molar ratio range of copper is (1 ~ 1.5): 1.
5. a kind of 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 DEG C, and pretreatment time is 3 ~ 10 hours.
6. a kind of 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 gaseous mixture, hydrogen and nitrogen mixture, and described heating rate is 10 ~ 20 DEG C/min, and sintering temperature is 600 ~ 900 DEG C, and sintering time is 4 ~ 15 hours; Described cooling method have cool with stove, Quenching in liquid nitrogen.
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