CN110391410A - A kind of preparation method of Copper-cladding Aluminum Bar tertiary cathode material - Google Patents
A kind of preparation method of Copper-cladding Aluminum Bar tertiary cathode material Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of Copper-cladding Aluminum Bar tertiary cathode material, the following steps are included: according to elemental mole ratios Ni:Co:Mn:Cu=x:y:z:1-x-y-z, soluble nickel salt, cobalt salt, manganese salt and mantoquita is taken to be configured to solution A, wherein 1/3≤x≤0.9,0≤y≤1/3,0≤z≤1/3,0≤1-x-y-z≤0.1;Complexing agent is taken to be configured to solution B;Precipitating reagent is taken to be configured to solution C;Complexing agent aqueous solution is added into reaction kettle as bottom liquid;Above-mentioned solution is added in reaction kettle, control pH is 10~11.6, and reaction temperature is 50~55 DEG C, stirring, under the protection of inert gas, coprecipitation reaction, after, product is filtered, is dried after washing to neutrality, obtains presoma M;Presoma M and lithium salts is taken to mix, carry out logical oxygen sintering, calcined temperature is 520~550 DEG C, 3~4.5h of burn-in time, sintering temperature are 820~849 DEG C, 10~14h of sintering time, heating rate is 4~6 DEG C/min, Copper-cladding Aluminum Bar tertiary cathode material is made, is suitble to industrialization large-scale production, product stable electrochemical property.
Description
Technical field
The present invention relates to electrode material technical field, in particular to a kind of preparation method of Copper-cladding Aluminum Bar tertiary cathode material.
Background technique
Now synthesize Copper-cladding Aluminum Bar tertiary cathode material (LinNixCoyMnzCu1-x-y-zO2, wherein 1≤n≤1.2,1/3≤x≤
0.9,0≤y≤1/3,0≤z≤1/3,0≤1-x-y-z≤0.1) method mainly have sol-gel method and solid sintering technology.
The process of sol-gal process synthesis Copper-cladding Aluminum Bar tertiary cathode material: quantitative Mn is weighed by molar ratio needed for product
(CH3COO)2·4H2O、Co(CH3COO)2·4H2O、Ni(CH3COO)2·4H2O、Li(CH3COO)·2H2O、Cu(CO2CH3)
2·H2O is dissolved in deionized water 50mL, 5% or more lithium acetate.Then suitable citric acid solution is added in the above solution
(citric acid/transition metal mole ratio is 1:1), acquired solution heats at 80 DEG C, and stirring is until form hydrogel.Then by water
Gel is placed in 120 DEG C of vacuum oven 12 hours.Dry gained gel mortar grinder is uniform, transfers in 500 DEG C of temperature
Enter in smelting furnace 3 hours, then obtained powder is regrind, 12h is calcined again at 850 DEG C, obtains final product
LinNixCoyMnzCu1-x-y-zO2。
Solid-phase sintering rule is relatively simple, only need to by product molar than weigh quantitative nickel salt, manganese salt, cobalt salt, mantoquita and
Lithium salts, it is with mortar that its mix grinding is uniform, carry out high temperature sintering.It generally is sintered reaction using Muffle furnace, process is divided into two
Point: 5h and 900 DEG C of sintering 16h of 500 DEG C of pre-sinterings.Sintered product is dry after washing, can obtain final required product.
The prior art is mainly the sol-gel method and solid sintering technology that experimental study uses.Wherein, sol-gel method
Synthesis cycle it is long, synthesis technology is relative complex, and at high cost, the difficulty for industrializing generation is bigger.Be not suitable for industrialization
Large-scale production.Solid sintering technology mainly uses mechanical means to carry out the mixing and refinement of raw material, easily leads to raw material micro Distribution
Unevenly, diffusion process is made to be difficult to successfully carry out, meanwhile, the impurity that induces one, and calcination temperature are easy in mechanical thinning process
Height, calcination time is long, and energy consumption is high, and lithium loss is serious, it is difficult to control stoichiometric ratio, easily formation miscellaneous phase, product is in composition, knot
There are larger differences for structure, size distribution etc., cause product chemical property unstable.
The present invention is directed to improve homogeneous tertiary cathode material in the above problem present on chemical property, one kind is provided
The preparation method of Copper-cladding Aluminum Bar tertiary cathode material.
Summary of the invention
Mirror is with this, and the present invention proposes a kind of preparation method of Copper-cladding Aluminum Bar tertiary cathode material, and synthesis cycle is relatively short, closes
It is relatively easy at technique, it is at low cost, it is suitble to industrialization large-scale production, and Copper-cladding Aluminum Bar tertiary cathode material electrochemistry is made
The excellent and stability of energy is good.
The technical scheme of the present invention is realized as follows: a kind of preparation method of Copper-cladding Aluminum Bar tertiary cathode material, including with
Lower step:
(1) according to elemental mole ratios Ni:Co:Mn:Cu=x:y:z:1-x-y-z, soluble nickel salt, soluble cobalt are weighed
Salt, soluble manganese salt and soluble copper salt are configured to solution A, wherein 1/3≤x≤0.9,0≤y≤1/3,0≤z≤1/3,0≤
1-x-y-z≦0.1;
Complexing agent is taken to be configured to solution B;
Precipitating reagent is taken to be configured to solution C;
(2) enveloping agent solution is added into reaction kettle as bottom liquid;Solution A, solution B and solution C are added in reaction kettle,
The pH for controlling reaction system is 10~11.6, and reaction temperature is 50~55 DEG C, is stirred, under the protection of inert gas, into
Reaction product is filtered by row coprecipitation reaction after reaction, obtains sediment, is washed with deionized to neutrality, will
Washed presoma is dried, the presoma M of the Copper-cladding Aluminum Bar tertiary cathode material after being dried;
(3) it taking presoma M and lithium salts to mix, carries out logical oxygen sintering, calcined temperature is 520~550 DEG C, burn-in time 3~
4.5h, sintering temperature are 820~849 DEG C, 10~14h of sintering time, and heating rate is 4~6 DEG C/min;After sintering, obtain
To Copper-cladding Aluminum Bar tertiary cathode material.
Preferably, in step (1), the complexing agent is at least one of ammonium hydroxide, ammonium carbonate, and the precipitating reagent is hydroxide
At least one of sodium, potassium hydroxide.
Preferably, in step (1), the concentration of the solution A is 2~3mol/L;The concentration of the solution B be 0.5~
3mol/L, the concentration of the solution C are 1~10mol/L, 0.5~1.5mol/L of concentration of the bottom liquid.
Preferably, in step (2), the control total ammonia density of reaction system is 0.5~1.5mol/L.
Preferably, in step (2), a is the constant greater than 0, and the volume of the reaction kettle is 5a L, and the volume of solution A is
1a~2a L, the volume of solution B are 0.5a L, and the volume of the bottom liquid is 1.5a~2.5a L.
Preferably, in step (2), feed flow rate≤3mL/min of the solution A, the feed flow rate of the solution B is≤
1.2mL/min, feed flow rate≤3mL/min of the solution C.
Preferably, in step (2), the mixing speed is 600~950rmp/min.
Preferably, in step (2), the coprecipitation reaction time is 20~48h.
Preferably, in step (2), the drying temperature is 60~100 DEG C, and drying time is 10~16h.
Preferably, in step (3), the material mol ratio of the presoma M and lithium salts is 1:1~1.2.
Compared with prior art, the beneficial effects of the present invention are:
(1) preparation method of Copper-cladding Aluminum Bar tertiary cathode material of the present invention, synthesis cycle is relatively short, and synthesis technology is relatively simple
It is single, it is at low cost, it is suitble to industrialization large-scale production, and Copper-cladding Aluminum Bar tertiary cathode material electrochemical performance and stabilization is made
Property is good.
(2) compared with homogeneous tertiary cathode material, the present invention mixes a small amount of copper, and the price of copper is lower than cobalt, saves cost, together
When be obviously improved the chemical property of synthetic material again.
(3) relative to other methods, other methods are primarily adapted for use in laboratory research, are not suitable for industrialized production,
The present invention is suitble to industrialization large-scale production, saves extra research and development time and cost.
Detailed description of the invention
Fig. 1 is the SEM figure that Copper-cladding Aluminum Bar tertiary cathode material is made in the embodiment of the present invention 1.
Top curve is the 4.4 V-1 C cyclic curves that Copper-cladding Aluminum Bar tertiary cathode material is made in the embodiment of the present invention 1 in Fig. 2
Figure, lower curve are the tertiary cathode material LiNi of not cupric0.6Co0.2Mn0.2O24.4 V-1 C cyclic curve figures.
Specific embodiment
In order to be best understood from the technology of the present invention content, specific embodiment is provided below, the present invention is described further.
Experimental method used in the embodiment of the present invention is conventional method unless otherwise specified.
Material used in the embodiment of the present invention, reagent etc., are commercially available unless otherwise specified.
Embodiment 1
A kind of preparation method of Copper-cladding Aluminum Bar tertiary cathode material, comprising the following steps:
(1) electronic balance weighing NiSO is used4·6H2O、CoSO4·7H2O、MnSO4·H2O、CuSO4·5H2O makes its mole
Than n (Ni:Co:Mn:Cu)=0.59:0.2:0.2:0.01, the mixed metal that deionized water is configured to 1.5L, 2.5mol/L is added
Solution;
It takes ammonium hydroxide as complexing agent, is dissolved in deionized water, be configured to 0.5 L, the solution B that concentration is 3mol/L;
It takes sodium hydroxide as precipitating reagent, is dissolved in deionized water, be configured to the solution C that concentration is 10mol/L;
(2) 2L, 0.9mol/L ammonia spirit are added into 5L reaction kettle as bottom liquid;Solution A, solution B and solution C are existed
Under the control of peristaltic pump, at the uniform velocity in addition reaction kettle, feed flow rate≤3mL/min of solution A, the feed flow rate of solution B are controlled
For≤1.2mL/min, feed flow rate≤3mL/min of solution C, while controlling solution A and solution B charging finishes time consistency;
The control total ammonia density of reaction system is 0.5~1.5mol/L, and the pH for controlling reaction system is 11.2 ± 0.01, reaction temperature 50
DEG C, mixing speed 800rmp/min carries out coprecipitation reaction for 24 hours under the protection of nitrogen gas, after reaction, will be anti-
Answer product Ni0.59Co0.2Mn0.2Cu0.01(OH)2Suspension pours into Buchner funnel, uses deionization under the suction filtration of vacuum pump using circulatory water
Water is washed, until filtrate is in neutrality;By washed Ni0.59Co0.2Mn0.2Cu0.01(OH)2Presoma is placed in 60 DEG C of constant temperature
Air dry oven dries 12h, the presoma M of the Copper-cladding Aluminum Bar tertiary cathode material after being dried;
(3) LiOHH is weighed with electronic balance2O, so that presoma M and Li material mol ratio 1:1.05, it will with mortar
LiOH·H2O and presoma are sufficiently mixed uniformly, by uniformly mixed presoma and LiOHH2The mixing of O is put into Muffle furnace,
Logical oxygen sintering is carried out, is warming up to 520 DEG C, pre-burning 4.5h with 5 DEG C/min rate, then be warming up to 820 DEG C with 5 DEG C/min rate, height
Temperature sintering 14h;After sintering, Copper-cladding Aluminum Bar tertiary cathode material LiNi is obtained0.59Co0.2Mn0.2Cu0.01O2。
Fig. 1 is as it can be seen that Copper-cladding Aluminum Bar tertiary cathode material of the present invention has α-NaFeO2Layer structure, pattern are spherical.
Fig. 2 is as it can be seen that Copper-cladding Aluminum Bar tertiary cathode material chemical property of the present invention is substantially better than the tertiary cathode material of not cupric
Material.
Embodiment 2
A kind of preparation method of Copper-cladding Aluminum Bar tertiary cathode material, comprising the following steps:
(1) electronic balance weighing NiSO is used4·6H2O、CoSO4·7H2O、MnSO4·H2O、CuSO4·5H2O makes its mole
Than n (Ni:Co:Mn:Cu)=0.6:0.17:0.2:0.03, the mixed metal that addition deionized water is configured to 1.5L, 2mol/L is molten
Liquid;
It takes ammonium hydroxide as complexing agent, is dissolved in deionized water, be configured to the solution B that concentration is 0.5 L, 2mol/L;
It takes sodium hydroxide as precipitating reagent, is dissolved in deionized water, be configured to the solution C that concentration is 8mol/L;
(2) 2L, 1mol/L ammonia spirit are added into 5L reaction kettle as bottom liquid;By solution A, solution B and solution C compacted
Under the control of dynamic pump, at the uniform velocity in addition reaction kettle, feed flow rate≤3mL/min of solution A is controlled, the feed flow rate of solution B is
≤ 1.2mL/min, feed flow rate≤3mL/min of solution C, at the same control solution A and solution B charging finish time consistency;Control
The total ammonia density of reaction system processed is 0.5~1.5mol/L, and the pH for controlling reaction system is 11.2 ± 0.01, reaction temperature 50
DEG C, mixing speed 800rmp/min carries out coprecipitation reaction for 24 hours under the protection of nitrogen gas, after reaction, will be anti-
Answer product Ni0.6Co0.17Mn0.2Cu0.03(OH)2Suspension pours into Buchner funnel, uses deionization under the suction filtration of vacuum pump using circulatory water
Water is washed, until filtrate is in neutrality;Washed presoma is placed in the dry 12h of 60 DEG C of constant temperature blast drying ovens, is obtained
The Ni of Copper-cladding Aluminum Bar tertiary cathode material after drying0.6Co0.17Mn0.2Cu0.03(OH)2Presoma M;
(3) LiOHH is weighed with electronic balance2O, so that presoma M and Li material mol ratio 1:1.05, it will with mortar
LiOH·H2O and presoma are sufficiently mixed uniformly, by uniformly mixed presoma and LiOHH2The mixing of O is put into Muffle furnace,
Logical oxygen sintering is carried out, is warming up to 520 DEG C, pre-burning 4.5h with 5 DEG C/min rate, then be warming up to 820 DEG C with 5 DEG C/min rate, height
Temperature sintering 14h;After sintering, Copper-cladding Aluminum Bar tertiary cathode material LiNi is obtained0.6Co0.17Mn0.2Cu0.03O2, the material is with α-
NaFeO2Layer structure, pattern are spherical in shape or spherical.
Embodiment 3
A kind of preparation method of Copper-cladding Aluminum Bar tertiary cathode material, comprising the following steps:
(1) electronic balance weighing NiSO is used4·6H2O、CoSO4·7H2O、MnSO4·H2O、CuSO4·5H2O makes its mole
Than n (Ni:Co:Mn:Cu)=0.33:0.33:0.33:0.01, the mixed metal that addition deionized water is configured to 1L, 3mol/L is molten
Liquid;
It takes ammonium hydroxide as complexing agent, is dissolved in deionized water, be configured to the solution B that concentration is 0.5 L, 3mol/L;
It takes sodium hydroxide as precipitating reagent, is dissolved in deionized water, be configured to the solution C that concentration is 5mol/L;
(2) 1.5L, 1mol/L ammonia spirit are added into 5L reaction kettle as bottom liquid;Solution A, solution B and solution C are existed
Under the control of peristaltic pump, at the uniform velocity in addition reaction kettle, feed flow rate≤3mL/min of solution A, the feed flow rate of solution B are controlled
For≤1.2mL/min, feed flow rate≤3mL/min of solution C, while controlling solution A and solution B charging finishes time consistency;
The control total ammonia density of reaction system is 0.5~1.5mol/L, and the pH for controlling reaction system is 10.1 ± 0.01, reaction temperature 55
DEG C, mixing speed 600rmp/min carries out coprecipitation reaction for 24 hours under the protection of nitrogen gas, after reaction, will be anti-
Answer product Ni0.33Co0.33Mn0.33Cu0.01(OH)2Suspension pours into Buchner funnel, spent under the suction filtration of vacuum pump using circulatory water from
Sub- water is washed, until filtrate is in neutrality;Washed presoma is placed in the dry 10h of 100 DEG C of constant temperature blast drying ovens, is obtained
The Ni of Copper-cladding Aluminum Bar tertiary cathode material after to drying0.33Co0.33Mn0.33Cu0.01(OH)2Presoma M;
(3) LiOHH is weighed with electronic balance2O, so that presoma M and Li material mol ratio 1:1, it will with mortar
LiOH·H2O and presoma are sufficiently mixed uniformly, by uniformly mixed presoma and LiOHH2The mixing of O is put into Muffle furnace,
Logical oxygen sintering is carried out, is warming up to 550 DEG C, pre-burning 3h with 4 DEG C/min rate, then be warming up to 849 DEG C with 6 DEG C/min rate, high temperature
It is sintered 10h;After sintering, Copper-cladding Aluminum Bar tertiary cathode material Li Ni is obtained0.33Co0.33Mn0.33Cu0.01O2, the material is with α-
NaFeO2Layer structure, pattern are spherical in shape or spherical.
Embodiment 4
A kind of preparation method of Copper-cladding Aluminum Bar tertiary cathode material, comprising the following steps:
(1) electronic balance weighing NiSO is used4·6H2O、CoSO4·7H2O、MnSO4·H2O、CuSO4·5H2O makes its mole
Than n (Ni:Co:Mn:Cu)=0.8:0.05:0.05:0.1, the mixed metal that addition deionized water is configured to 3L, 2.5mol/L is molten
Liquid;
It takes ammonium hydroxide as complexing agent, is dissolved in deionized water, be configured to the solution B that concentration is 1 L, 2.5mol/L;
It takes potassium hydroxide as precipitating reagent, is dissolved in deionized water, be configured to the solution C that concentration is 8mol/L;
(2) 3L, 1.2mol/L ammonia spirit are added into 10L reaction kettle as bottom liquid;By solution A, solution B and solution C
Under the control of peristaltic pump, at the uniform velocity in addition reaction kettle, feed flow rate≤3mL/min of solution A, the feeding flow of solution B are controlled
Speed for≤1.2mL/min, feed flow rate≤3mL/min of solution C, while control solution A and solution B charging finish the time one
It causes;The control total ammonia density of reaction system is 0.5~1.5mol/L, and the pH for controlling reaction system is 11.5 ± 0.01, reaction temperature
It is 55 DEG C, mixing speed 950rmp/min, under the protection of nitrogen gas, carries out coprecipitation reaction 48h, after reaction,
By reaction product Ni0.8Co0.05Mn0.05Cu0.1(OH)2Suspension pours into Buchner funnel, spends under the suction filtration of vacuum pump using circulatory water
Ionized water is washed, until filtrate is in neutrality;Washed presoma is placed in the dry 16h of 60 DEG C of constant temperature blast drying ovens,
The Ni of Copper-cladding Aluminum Bar tertiary cathode material after being dried0.8Co0.05Mn0.05Cu0.1Presoma M;
(3) LiOHH is weighed with electronic balance2O, so that presoma M and Li material mol ratio 1:1.2, it will with mortar
LiOH·H2O and presoma are sufficiently mixed uniformly, by uniformly mixed presoma and LiOHH2The mixing of O is put into Muffle furnace,
Logical oxygen sintering is carried out, is warming up to 520 DEG C, pre-burning 4h with 6 DEG C/min rate, then be warming up to 820 DEG C with 4 DEG C/min rate, high temperature
It is sintered 12h;After sintering, Copper-cladding Aluminum Bar tertiary cathode material Li Ni is obtained0.8Co0.05Mn0.05Cu0.1O2, the material is with α-
NaFeO2Layer structure, pattern are spherical in shape or spherical.
Comparative example 1
This comparative example the difference from embodiment 1 is that, in step (1), without containing CuSO is not added4·5H2O, and
NiSO4·6H2O、CoSO4·7H2O、MnSO4·H2Molar ratio n (Ni:Co:Mn)=0.5:0.2:0.3 of O, other step 1
It causes, tertiary cathode material LiNi is made0.5Co0.2Mn0.3O2。
Comparative example 2
This comparative example the difference from embodiment 1 is that, in step (1), NiSO4·6H2O、CoSO4·7H2O、MnSO4·
H2O、CuSO4·5H2O makes its molar ratio n (Ni:Co:Mn:Cu)=0.6:0.1:0.1:0.2.That is 1-x-y-z > 0.1, other
Step is consistent, obtains Copper-cladding Aluminum Bar tertiary cathode material LiNi0.6Co0.1Mn0.1Cu0.2O2。
Comparative example 3
This comparative example the difference from embodiment 1 is that, in step (3), pre-burning is not carried out, directly with 5 DEG C/min rate liter
Temperature is to 750 DEG C, high temperature sintering 18h.
Comparative example 4
This comparative example the difference from embodiment 1 is that, in step (3), be warming up to 600 DEG C with 8 DEG C/min rate, pre-burning
5h, then 900 DEG C are warming up to 10 DEG C/min rate, high temperature sintering 15h.
One, tertiary cathode material made from Examples 1 to 4 and comparative example 1~4 is tested for the property, in 4.4 V 1
The condition test of C (1C=200mA/g), test result is as follows:
The above results show that 1~4 tap density of the embodiment of the present invention is strong, and discharge capacity is higher for the first time, 50 circulation volumes
Conservation rate, 100 circulation volume conservation rates are excellent, excellent in stability.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of Copper-cladding Aluminum Bar tertiary cathode material, which comprises the following steps:
(1) according to elemental mole ratios Ni:Co:Mn:Cu=x:y:z:1-x-y-z, weigh soluble nickel salt, soluble cobalt, can
Dissolubility manganese salt and soluble copper salt are configured to solution A, wherein 1/3≤x≤0.9,0≤y≤1/3,0≤z≤1/3,0≤1-x-y-
z≦0.1;
Complexing agent is taken to be configured to solution B;
Precipitating reagent is taken to be configured to solution C;
(2) enveloping agent solution is added into reaction kettle as bottom liquid;Solution A, solution B and solution C are added in reaction kettle, control
The pH of reaction system is 10~11.6, and reaction temperature is 50~55 DEG C, is stirred, under the protection of inert gas, is total to
Reaction product is filtered by precipitation reaction after reaction, obtains sediment, is washed with deionized to neutrality, will be washed
Presoma dried, the presoma M of the Copper-cladding Aluminum Bar tertiary cathode material after being dried;
(3) it taking presoma M and lithium salts to mix, carries out logical oxygen sintering, calcined temperature is 520~550 DEG C, 3~4.5h of burn-in time,
Sintering temperature is 820~849 DEG C, 10~14h of sintering time, and heating rate is 4~6 DEG C/min;After sintering, obtains copper and mix
Miscellaneous tertiary cathode material.
2. the preparation method of Copper-cladding Aluminum Bar tertiary cathode material according to claim 1, which is characterized in that in step (1), institute
Stating complexing agent is at least one of ammonium hydroxide, ammonium carbonate, and the precipitating reagent is at least one of sodium hydroxide, potassium hydroxide.
3. the preparation method of Copper-cladding Aluminum Bar tertiary cathode material according to claim 1 or 2, which is characterized in that step (1)
In, the concentration of the solution A is 2~3mol/L;The concentration of the solution B is 0.5~3mol/L, and the concentration of the solution C is 1
~10mol/L, 0.5~1.5mol/L of concentration of the bottom liquid.
4. the preparation method of Copper-cladding Aluminum Bar tertiary cathode material according to claim 1, which is characterized in that in step (2), control
The total ammonia density of reaction system processed is 0.5~1.5mol/L.
5. the preparation method of Copper-cladding Aluminum Bar tertiary cathode material according to claim 3, which is characterized in that in step (2), a
For the constant greater than 0, the volume of the reaction kettle is 5a L, and the volume of solution A is 1a~2a L, and the volume of solution B is 0.5a
L, the volume of the bottom liquid are 1.5a~2.5a L.
6. the preparation method of Copper-cladding Aluminum Bar tertiary cathode material according to claim 5, which is characterized in that in step (2), institute
Feed flow rate≤3mL/min of solution A is stated, the feed flow rate of the solution B is≤1.2mL/min, the feeding flow of the solution C
Speed≤3mL/min.
7. the preparation method of Copper-cladding Aluminum Bar tertiary cathode material according to claim 1, which is characterized in that in step (2), institute
Stating mixing speed is 600~950rmp/min.
8. the preparation method of Copper-cladding Aluminum Bar tertiary cathode material according to claim 1 or claim 7, which is characterized in that step (2)
In, the coprecipitation reaction time is 20~48h.
9. the preparation method of Copper-cladding Aluminum Bar tertiary cathode material according to claim 1, which is characterized in that in step (2), institute
Stating drying temperature is 60~100 DEG C, and drying time is 10~16h.
10. the preparation method of described in any item Copper-cladding Aluminum Bar tertiary cathode materials according to claim 1~9, which is characterized in that step
Suddenly in (3), the material mol ratio of the presoma M and lithium salts is 1:1~1.2.
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