CN111816850A - Method for forming lithium-containing spherical precursor of lithium battery positive electrode material - Google Patents
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Abstract
The invention discloses a method for manufacturing and forming a lithium-containing spherical precursor of a lithium battery anode material, which mainly comprises the following steps: uniformly mixing the lithium-containing metal salt ion containing acid radical with water solution to prepare lithium-containing metal salt aqueous solution; feeding the lithium-containing metal salt aqueous solution into a hot air furnace chamber arranged in high-temperature spray granulation equipment, and spraying and diffusing the lithium-containing metal salt aqueous solution fed into the hot air furnace chamber into an atomized state through an atomizer so as to form a plurality of spherical liquid drops with the particle size of 0.1-20 microns; high-temperature hot air with the temperature between 300 ℃ and 1000 ℃ is supplied in the hot air furnace chamber, so that the atomized spherical liquid drops and the high-temperature hot air act to generate a cracking effect to crack acid radicals, and the spherical liquid drops are instantly dried and shaped to form the lithium-containing spherical precursor.
Description
Technical Field
The present invention relates to a precursor process technology of lithium battery anode material; in particular to a novel manufacturing and forming method of lithium-containing spherical precursor for positive electrode material of lithium battery.
Background
Rechargeable lithium batteries are widely used in various portable electronic devices due to their high energy density; as for electrode materials of lithium batteries, LiCoO is used2The cathode material is quite expensive, and currently, the LNMCO type cathode material is widely used to replace the LNMCO type cathode material, which means the oxide of lithium-nickel-manganese-cobalt, the LNMCO type cathode material has the advantage that the raw material price of the component M is much lower than that of Co, and the addition of lithium can increase the discharge capacity.
For the production of cathode materials containing composite compositions, special precursors are usually used, and in order to achieve high performance without excessive sintering, the cathode precursors need to contain the transition metals in a well-mixed form, generally speaking, mixed hydroxides of suitable size and morphology are usually obtained by precipitation reactions: (1) under the condition of controlled pH value, utilizing any one of sodium hydroxide flow, lithium hydroxide flow or potassium hydroxide flow and mixed metal salt flow to precipitate mixed hydroxide in the reactor; (2) removing the precursor suspension and filtering; (3) the filtered wet cake mass is dried under set conditions.
As mentioned above, the precursors of the conventional lithium battery cathode material are mainly prepared by precipitation, however, the problem of the preparation method is mainly caused by the hydroxyl (OH) radical in the process-) The reaction precipitation produces waste water, which causes environmental pollution if directly discharged, but the industrial industry must increase the cost greatly if the filter equipment is configured according to the current discharge standard, which does not meet the better industrial economic benefit.
Disclosure of Invention
The main purpose of the present invention is to provide a method for manufacturing a lithium-containing spherical precursor for a positive electrode material of a lithium battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for forming a lithium-containing spherical precursor of a lithium battery anode material mainly comprises the following steps: uniformly mixing the lithium-containing metal salt ions containing acid radicals with the water solution to prepare a lithium-containing metal salt water solution; feeding the lithium-containing metal salt aqueous solution into a hot air furnace chamber arranged in high-temperature spray granulation equipment, and spraying and diffusing the lithium-containing metal salt aqueous solution fed into the hot air furnace chamber into an atomized state through an atomizer so as to form a plurality of spherical liquid drops with the particle size of 0.1-20 mu m; and supplying high-temperature hot air with the temperature of 300-1000 ℃ in a hot air furnace chamber, so that the atomized spherical liquid drops and the high-temperature hot air act to generate a cracking effect to crack acid radicals, and instantly drying and shaping each spherical liquid drop to form the lithium-containing spherical precursor.
The main effects and advantages of the present invention include:
firstly, compared with the prior art, the method adopts hydroxyl (OH)-) The precipitation method needs a large amount of water for reaction and generates waste water after reaction, and the invention uses the technical characteristics of high-temperature hot air cracking acid radicals in a hot air furnace chamber to instantly dry and shape each spherical liquid drop and evaporate water to prepare the lithium-containing spherical precursor, so that the process only generates waste gas and does not generate waste water, the setting cost of waste water purification equipment can be saved, and the method has the advantages of water and energy saving, thereby achieving better industrial economic benefit of greatly reducing the cost of manufacturing the lithium-containing precursor.
Secondly, the lithium-containing spherical precursor of the invention approaches the surface contour shape of the sphere, which can greatly increase the contact area between the precursor and other components (such as lithium carbonate and lithium hydroxide) during the subsequent sintering, thereby greatly increasing the sintering quality and effect, and relatively improving the yield, efficiency, electric storage capacity and other advantages and practical advancement of the lithium ion battery anode material.
Another object of the present invention is to provide a nozzle atomizer, which is equipped with a circulating cooling mechanism to properly cool the nozzle atomizer, thereby avoiding nozzle clogging.
The present invention further provides another technical feature of a furnace wall hammering means in the process of the third step, so as to knock down the material stuck on the furnace wall of the hot-air furnace chamber, thereby achieving the advantage of further increasing the yield of the lithium-containing spherical precursor product and the practical improvement.
Drawings
FIG. 1 is a schematic view of a high temperature spray granulation apparatus according to a preferred embodiment of the present invention.
FIG. 2 is a schematic view of the internal operation of the high-temperature spray granulation apparatus according to the preferred embodiment of the present invention.
FIG. 3 is an enlarged view of the portion B of FIG. 2.
FIG. 4 is an enlarged cross-sectional view of the atomizer of the present invention.
FIG. 5 is a view showing an embodiment of the atomizer of the present invention provided with a circulation cooling mechanism.
FIG. 6 is a SEM image of a lithium-containing spherical precursor of the present invention.
FIG. 7 is a SEM of a precursor of the prior art.
Detailed Description
Referring to fig. 1, 2, 3 and 4, a preferred embodiment of the method for forming the lithium-containing spherical precursor of the positive electrode material of the lithium battery of the present invention is shown, but these embodiments are only for illustrative purposes and are not limited to this structure in the patent application.
The method for preparing and forming the lithium-containing spherical precursor of the lithium battery anode material comprises the following steps: the first step is as follows: uniformly mixing a lithium-containing metal salt ion A containing acid radicals with a water solution B to prepare a lithium-containing metal salt water solution 10; step two: feeding the lithium-containing metal salt aqueous solution 10 into a hot air furnace chamber 21 of a high temperature spray granulation device 20, spraying and diffusing the lithium-containing metal salt aqueous solution 10 fed into the hot air furnace chamber 21 through an atomizer 24 of the high temperature spray granulation device 20 to form a plurality of spherical droplets 50 with the particle size of 0.1-20 μm; (as shown in FIG. 3) step three: supplying high temperature hot air 22 with a temperature between 300 ℃ and 1000 ℃ into the hot air furnace chamber 21, so that the atomized plurality of spherical droplets 50 and the high temperature hot air 22 act to generate a cracking effect to crack acid radicals, and instantly drying and shaping each spherical droplet 50, thereby forming the lithium-containing spherical precursor 40 (as shown in fig. 6) (note: also called spherical powder of lithium-containing metal oxide).
Wherein the hot air 22 supplied from the hot air furnace chamber 21 is preferably within a range of 400 ℃ to 800 ℃.
Further, after the third step, a gas-particle separation step (for example, a pipe distribution dust collector 03, as shown in fig. 1) is further included to separate and guide the dried and shaped lithium-containing spherical precursor 40 and the exhaust gas; the gas-particle separation step further comprises a particle size screening step for screening and classifying the lithium-containing spherical precursor 40 with a set particle size; after the step of particle size screening, a mixed sintering step is also included, the lithium-containing spherical precursor 40 is taken out and dried, and then the dried lithium-containing spherical precursor 40 and lithium carbonate (Li)2CO3) Mixing to obtain a metal oxide mixture, and sintering the metal oxide mixture at a high temperature of 600-950 ℃ to obtain a lithium ion battery anode metal oxide material having the following general formula:
Li(0.92～0.99)(LiwMnxCoyNizAlr)O2wherein w + x + y + z + r is 1.
The lithium-containing spherical precursor 40 of the invention can make the precursor of the lithium ion battery anode metal oxide material contain lithium components at first and has a surface contour shape approaching to a sphere, and has the advantages that: because the lithium-containing uniformity of the precursor is high, the yield of the subsequent sintering can be greatly increased; because lithium is lost during sintering in the prior art, the lithium-containing composite material can contain lithium in a precursor, and the lithium loss during subsequent sintering can be calculated, so that the loss generated during secondary sintering is compensated; the cracking effect generated during the hot blast 22 in the hot blast furnace chamber 21 has another advantage: since each spherical droplet 50 reacts with the high-temperature hot air 22 to generate a cracking effect to crack acid radicals, the high-temperature hot air 22The cracking effect is generated during the process, which causes each spherical liquid drop 50 to be dried and shaped instantly and the water to evaporate, thus only generating waste gas such as O2、H2O and NO2No waste water is generated, and the waste gas can be purified and discharged by simple air filtering equipment, so that the equipment cost is greatly reduced, and the water consumption in the process of the invention is quite small, thereby having the environmental-friendly economic benefits of water saving and energy saving (note: the prior art adopts hydroxyl (OH)-) The precipitation method requires a large amount of water for reaction, and also causes waste water after reaction, and the purification equipment has a relatively high cost and is easy to cause pollution, which is an extended environmental problem).
As shown in fig. 6, a scanning electron microscope analysis chart of the lithium-containing spherical precursor 40 of the present invention is shown, in this example, the surface of the lithium-containing spherical precursor 40 approaches to a spherical and smooth shape, so that the powder stacking density can be effectively increased when the subsequent rolling process is performed, and the quality and effect of the battery positive plate can be greatly improved; fig. 7 is a scanning electron microscope analysis diagram of a precursor 60 product entity in the prior art, and the surface thereof is significantly rough and has greatly different contour shapes compared with the present invention, so that the stacking density of powder is not good when the rolling process is performed, and the quality and effect after the battery positive plate is manufactured are poor.
Wherein, the lithium-containing metal salt ion A containing acid radical adopts nickel, cobalt, aluminum and any combination of lithium/nickel, cobalt, manganese and lithium in the composition; the salt in the lithium-containing metal salt ion A composition is selected from Nitrate (NO)3 -) Sulfate (SO)4 2-) Or Carbonates (CO)3 2-) Any one of them.
Wherein, the lithium-containing metal salt aqueous solution 10 in the first step has the following general formula:
((1+w)Li(NO3)(s)+xMn(NO3)2(s)+yCo(NO3)2(s)+zNi(NO3)2(s)+rAl(NO3)3(s))+H2O
→((1+w)Li++xMn2++yCo2++zNi2++rAl3+)(l)+(1+w+2x+2y+2z+3r)(NO3)- (l)+H2O(l)
the lithium-containing spherical precursor 40 formed after the cracking in step three has the following general formula:
Li(0.95～1)(LiwMnxCoyNizAlr)O2(s)+(1+w+2x+2y+2z+3r)NO2(g)+H2O(g)
in the above general formula, w + x + y + z + r is 1.
As can be seen from the above general formula, when the spherical droplets 50 react with the high-temperature hot air 22 to generate the cracking effect, the acid groups thereof are cracked (2 NO)3 -→2NO2+O2) It can be seen that the final by-product of the process of the present invention is only gas.
As shown in fig. 4, the atomizer 24 of the high temperature spray granulation apparatus 20 is a nozzle atomizer; for purposes of illustration, the nozzle atomizer may be any of two-fluid, three-fluid, or four-fluid, with the number of air flow channels. As shown in fig. 5, in this embodiment, the atomizer 24 is further provided with a circulating cooling mechanism 30; the purpose of the circulation cooling mechanism 30 in this embodiment is mainly due to the relatively high temperature of the hot air oven chamber 21, which requires proper cooling to avoid nozzle clogging. Alternatively, the atomizer 24 of the high temperature spray granulation apparatus 20 may be an ultrasonic atomizer (not shown).
In addition, in the third step, a furnace wall hammering means (such as activating the air hammer 08 to knock the furnace wall) can be further performed to knock down the material stuck on the furnace wall of the hot blast furnace chamber 21, thereby increasing the yield of the lithium-containing spherical precursor 40.
In the present invention, in a specific application, referring to fig. 1, the method for forming the lithium-containing spherical precursor of the lithium battery positive electrode material may be implemented as the following steps: firstly, weighing (lithium nitrate, nickel nitrate, cobalt nitrate and manganese nitrate) or (lithium nitrate, nickel nitrate, cobalt nitrate and aluminum nitrate) and pouring into a stirring tank 06, then stirring in the stirring tank 06 for more than 30 minutes, and forming a lithium-containing metal salt aqueous solution 10 from the liquid after stirring; then, the following devices are started and operated:
(1) starting the exhaust fan 01 and setting the exhaust fan at 70 Hz;
(2) starting the air solenoid valve 02 to operate the atomizer 24;
(3) the cooling water tank 04 is started to avoid the overhigh heating temperature of the hot air furnace chamber 21;
(4) starting the gas burner 05 to heat the hot-blast furnace chamber 21 for about 1.5 to 2 hours, so that the temperature in the hot-blast furnace chamber 21 is 300 to 1000 ℃ (preferably 400 to 800 ℃), the outlet temperature is less than 180 ℃, the static pressure in the hot-blast furnace chamber 21 is 10 to 15mmAq, and the pressure in the atomizer 24 is 2 to 3kg/cm2；
After the hot air furnace chamber 21 is heated, the quantitative pump 07 is turned on to operate, and the flow rate is adjusted to 20ml/min to drive the lithium-containing metal salt aqueous solution 10 to be sent to the high temperature spray granulation equipment 20, and the temperature in the hot air furnace chamber 21 is kept to be higher than 450 ℃; when the lithium-containing metal salt aqueous solution 10 is sent to the high-temperature spray granulation equipment 20, the lithium-containing metal salt aqueous solution 10 sprayed from the nozzle of the atomizer 24 is mixed with the high-pressure gas 23 guided by another channel in the atomizer 24 (as shown in fig. 4), at this moment, the sprayed lithium-containing metal salt aqueous solution 10 can utilize the strong impact and turbulence of the high-pressure gas 23 to generate the effects of homogenization and fine granulation, so as to generate a plurality of spherical droplets 50 to be sprayed into the hot air furnace chamber 21; then, the high temperature hot air 22 in the hot air furnace chamber 21 is used to instantly dry each spherical liquid droplet 50 to form a lithium-containing spherical precursor 40; at this time, the air hammer 08 is started and hits the lithium-containing spherical precursor 40 stuck on the wall of the hot-air furnace chamber 21; finally, collecting the lithium-containing spherical precursor 40 by a pipe distribution dust collector 03; the exhaust gas generated in the process is exhausted by the exhaust fan 01, and the dried lithium-containing spherical precursor 40 and lithium carbonate (Li)2CO3) Mixing to obtain a metal oxide mixture, and sintering the metal oxide mixture at 600-950 ℃ to obtain the lithium ion battery anode metal oxide material Li(0.92～0.99)(LiwMnxCoyNizAlr)O2Wherein w + x + y + z + r is 1.
Furthermore, the forming method of the present invention can be implemented according to different relevant standard process specifications of various countries in the world, for example, the countries of japan and europe generally adopt the NCA process, and the aqueous solution of the metal salt thereof contains NiCoAl (nickel, cobalt, aluminum); regarding taiwan, china and korea usually adopt NCM process, and the metal salt aqueous solution thereof contains NiCoMn (nickel, cobalt and manganese), the following further explains the concrete composition ratio and process brief step embodiments of the lithium-containing ball precursor manufacturing and forming technology of the lithium battery positive electrode material of the present invention applied to different process basic structures:
< specific examples 1 to 1>
Weighing lithium nitrate, nickel nitrate, cobalt nitrate and manganese nitrate according to the molar ratio of 1.08:0.34: 0.08: 0.5, uniformly mixing and dissolving the four raw materials in water to form the lithium-containing metal salt aqueous solution 10, wherein the added lithium nitrate is 161.88g, the nickel nitrate is 214.93g, the cobalt nitrate is 50.61g and the manganese nitrate is 311.89g, injecting the lithium-containing metal salt aqueous solution 10 into a hot air furnace chamber 21 of a high-temperature spray granulation device 20, and controlling the optimal temperature of the hot air furnace chamber 21 to be 400-800 ℃ to generate the lithium-containing spherical precursor 40Li(0.95～1)(Li0.08Ni0.34Co0.08Mn0.5)O2. Then the lithium-containing spherical precursor 40 is sintered for 10 hours at 900 ℃ to obtain the lithium ion battery anode metal oxide material Li(0.92～0.99)(Li0.08Ni0.34Co0.08Mn0.5)O2The material ratios are summarized below (Table 1-1).
< examples 1 and 2>
To be provided with<Examples 1-1>The lithium ion battery anode metal oxide material is prepared in the same way, and the main differences are as follows: the four raw materials of lithium nitrate, nickel nitrate, cobalt nitrate and manganese nitrate are weighed according to the molar ratio of 1.03:0.80:0.10:0.07, the added lithium nitrate is 154.39g, the added nickel nitrate is 505.72g, the added cobalt nitrate is 63.27g, and the added manganese nitrate is43.66g, the lithium-containing spherical precursor 40Li was produced(0.95～1)(Li0.03Ni0.8Co0.1Mn0.07)O2. Then the lithium-containing spherical precursor 40 is sintered at 800 ℃ for 10 hours with the temperature maintained, and the lithium ion battery anode metal oxide material Li can be obtained(0.92～0.99)(Li0.03Ni0.8Co0.1Mn0.07)O2And the material ratios are summarized below (tables 1-2).
< examples 1 to 3>
To be provided with<Examples 1-1>The lithium ion battery anode metal oxide material is prepared in the same way, and the main differences are as follows: lithium nitrate, nickel nitrate, cobalt nitrate and aluminum nitrate are weighed according to the molar ratio of 1.01:0.85:0.11:0.03, 70.15g of lithium nitrate, 248.97g of nickel nitrate, 32.25g of cobalt nitrate and 11.34g of aluminum nitrate are added, and the produced lithium-containing spherical precursor 40Li is(0.95～1)(Li0.01Ni0.85Co0.11Al0.03)O2. Then the lithium-containing spherical precursor 40 is sintered at 800 ℃ for 10 hours with the temperature maintained, and the obtained lithium ion battery anode metal oxide material is Li(0.92～0.99)(Li0.01Ni0.85Co0.11Al0.03)O2The material ratios are summarized below (tables 1-3).
TABLE I preparation of Li-containing spherical precursor Li (Li)wMnxCoyNizAlr)O2The ratio of the powder to the solution
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (11)
1. A method for forming a lithium-containing spherical precursor of a lithium battery anode material is characterized by comprising the following steps:
the method comprises the following steps: uniformly mixing a lithium-containing metal salt ion containing acid radical with a water solution to prepare a lithium-containing metal salt water solution;
step two: feeding the lithium-containing metal salt aqueous solution into a hot air furnace chamber arranged in high-temperature spray granulation equipment, and spraying and diffusing the lithium-containing metal salt aqueous solution fed into the hot air furnace chamber into an atomized state through an atomizer arranged in the high-temperature spray granulation equipment so as to form a plurality of spherical liquid drops with the particle size of 0.1-20 mu m;
step three: supplying high-temperature hot air with the temperature of 300-1000 ℃ in the hot air furnace chamber, so that the atomized plurality of spherical liquid drops and the high-temperature hot air act to generate a cracking effect to crack acid radicals, and instantly drying and shaping each spherical liquid drop, thereby forming the lithium-containing spherical precursor.
2. The method of claim 1, wherein the lithium-containing metal salt ion containing acid groups is selected from the group consisting of nickel, cobalt, aluminum, and lithium/any combination of nickel, cobalt, manganese, and lithium; the salt in the lithium-containing metal salt ion composition is selected from one of nitrate, sulfate or carbonate.
3. The method of claim 2, wherein the step of forming the lithium-containing spherical precursor of the lithium battery positive electrode material comprises the following steps:
((1+w)Li++xMn2++yCo2++zNi2++rAl3+)(l)+(1+w+2x+2y+2z+3r)(NO3)- (l)+H2O(l)
furthermore, the lithium-containing spherical precursor formed in the third step has the following general formula:
Li(0.95～1)(LiwMnxCoyNizAlr)O2(s)+(1+w+2x+2y+2z+3r)NO2(g)+H2O(g)
in the above general formula, w + x + y + z + r is 1.
4. The method as claimed in claim 3, wherein the atomizer of the high temperature spray granulation equipment is a nozzle atomizer; the nozzle atomizer can select any one of two fluid, three fluid or four fluid air flow passage quantity.
5. The method as claimed in claim 4, wherein the atomizer further comprises a cooling circulation mechanism.
6. The method as claimed in claim 3, wherein the atomizer of the high temperature spray granulation equipment is an ultrasonic atomizer.
7. The method as claimed in claim 4 or 6, wherein the hot air supplied from the hot air furnace chamber is in a range of 400 ℃ to 800 ℃.
8. The method as claimed in claim 7, wherein a furnace-wall hammering means is further implemented to knock down the material stuck on the wall of the hot-air furnace chamber during the step three.
9. The method as claimed in claim 8, further comprising a step of separating the gas particles after the step three, wherein the dried and shaped lithium-containing spherical precursor and the exhaust gas are diverted.
10. The method as claimed in claim 9, further comprising a particle size sorting step after the gas particle separation step, wherein the particle size sorting step is performed to sort the lithium-containing spherical precursor.
11. The method as claimed in claim 9, wherein the step of screening the particle size further comprises a step of mixing and sintering, wherein the step of taking out the lithium-containing spherical precursor and drying the lithium-containing spherical precursor, mixing the dried lithium-containing spherical precursor with lithium carbonate to obtain a metal oxide mixture, and sintering the metal oxide mixture at a high temperature of 600 ℃ to 950 ℃ to obtain a lithium ion battery positive electrode metal oxide material having a general formula of Li(0.92～0.99)(LiwMnxCoyNizAlr)O2Wherein w + x + y + z + r is 1.
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| JP7289584B1 (en) * | 2023-03-10 | 2023-06-12 | 大川原化工機株式会社 | Large-capacity ultra-atomized spray-drying apparatus and large-capacity ultra-atomized spray-drying method |
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