CN114226340B - Method for removing residual alkali of high-nickel anode material by water washing and obtained anode material - Google Patents

Method for removing residual alkali of high-nickel anode material by water washing and obtained anode material Download PDF

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CN114226340B
CN114226340B CN202111555770.9A CN202111555770A CN114226340B CN 114226340 B CN114226340 B CN 114226340B CN 202111555770 A CN202111555770 A CN 202111555770A CN 114226340 B CN114226340 B CN 114226340B
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CN114226340A (en
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许开华
谢军
李伟
刘德宠
施杨
周晓燕
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GEM Wuxi Energy Materials Co Ltd
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

The invention discloses a method for removing residual alkali by washing a high-nickel anode material and an obtained anode material. The method for removing residual alkali by water washing of the high-nickel cathode material comprises the following steps: obtaining a high-nickel anode material primary sintering material; obtaining a carboxymethyl cellulose CMC-X solution; wherein CMC-X is a mixture of CMC-H and CMC-Li; and (3) washing the high-nickel anode material calcined material by using a carboxymethyl cellulose CMC-X solution, and performing solid-liquid separation and drying to obtain a dried material. According to the invention, by adding modified carboxymethyl cellulose CMC-X (X = H or Li) into water, the damage of washing to the material surface lattice is weakened through carboxymethyl cellulose lithium while removing residual alkali on the material surface, and simultaneously, the precipitation of lithium ions in an internal structure is inhibited in the drying process, the lattice stability of a high-nickel material is increased, and the capacity and the cycle performance of the material are improved.

Description

Method for removing residual alkali of high-nickel anode material by water washing and obtained anode material
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a method for removing residual alkali by washing a high-nickel anode material and an obtained anode material.
Background
In recent years, the new energy industry has been rapidly developed. The lithium ion battery is an energy storage device in new energy industry, and is widely applied to the fields of new energy automobiles, electric tools, energy storage power stations and the like. High nickel positive electrode materials belong to the class of lithium ion battery anodes because of their high energy density,The cost of low metal elements has become increasingly hot. The high-nickel anode material is sensitive to moisture and moisture, but is caused by LiOH and Li on the surface of the material 2 CO 3 The content is high, and the high nickel anode material is usually subjected to a water washing process in the synthesis process. The current common water washing method of the high-nickel anode material is to stir for a certain time according to a certain water-material ratio, then carry out suction filtration or filter pressing, and finally enter an oven for drying, and some methods are to add some additives, such as HF, boric acid and the like, into water. However, li in the crystal lattice of the material surface is easily caused in the water washing process + Dissolving out to generate NiO without electrochemical activity, destroying the surface phase structure of the material, also influencing the electrochemical performance of the material, and drying the material after water washing, wherein more water is still remained on the surface of the material, and lithium has hydrophilicity and is equivalent to Li supply in the drying process + The precipitation provides a "drag" force that results in a loss of material discharge capacity.
Disclosure of Invention
The invention aims to overcome the technical defects, provides a method for removing residual alkali by washing a high-nickel anode material and the obtained anode material, and solves the technical problems that the high-nickel anode material in the prior art has poor stability in a washing process and is easy to reduce the electrochemical performance of the anode material.
The invention provides a method for removing residual alkali from a high-nickel cathode material by water washing, which comprises the following steps of:
obtaining a first sintering material of the high-nickel anode material;
obtaining a carboxymethyl cellulose CMC-X solution; wherein CMC-X is a mixture of CMC-H and CMC-Li;
and (3) washing the high-nickel anode material calcined material by using a carboxymethyl cellulose CMC-X solution, and performing solid-liquid separation and drying to obtain a dried material.
The second aspect of the invention provides a high nickel cathode material, which is obtained by the method for removing residual alkali by water washing of the high nickel cathode material provided by the first aspect of the invention.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, by adding modified carboxymethyl cellulose CMC-X (X = H or Li) into water, while removing residual alkali on the surface of the material, damage of water washing to the surface lattice of the material is weakened through carboxymethyl cellulose lithium, and meanwhile, the precipitation of lithium ions in an internal structure is inhibited in the drying process, so that the lattice stability of the high-nickel material is increased, and the capacity and the cycle performance of the material are improved.
Drawings
FIG. 1 is an SEM image of high nickel cathode materials obtained in comparative example 1 and example 2 of the present invention;
FIG. 2 is a graph showing the charge and discharge curves of a sintered material according to the present invention and high nickel cathode materials obtained in comparative example 2 and example 3;
FIG. 3 is a graph showing cycle characteristics of the high nickel positive electrode materials obtained in comparative examples 1 to 2 and examples 2 to 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The first aspect of the invention provides a method for removing residual alkali by washing a high-nickel cathode material with water, which comprises the following steps:
s1, obtaining a high-nickel anode material primary sintering material;
s2, obtaining a carboxymethyl cellulose CMC-X solution; wherein CMC-X is a mixture of CMC-H and CMC-Li;
and S3, washing the high-nickel anode material calcined material by using a carboxymethyl cellulose CMC-X solution, and performing solid-liquid separation and drying to obtain a dried material.
CMC cellulose has been widely used in negative electrode material, is called carboxymethyl cellulose sodium (CMC-Na), is a derivative with ether structure obtained by chemical modification of natural cellulose, is a water-soluble hydrophilic colloid, is easily dissolved in water to prepare viscous solution, has good stability, almost has no change of viscosity after long-term storage, and does not dissolve like inorganic salt to dissociate positive and negative ions, CMC particles are firstly suspended in aqueous solution, and then are highly polymerizedUnder the action of water molecules, the CMC molecular chain slowly opens the inner hydrogen bonds among the molecules to perform hydration, and finally forms colloid. In the process of washing the high-nickel cathode material, the inventor finds that if CMC-H is singly adopted as an additive in the process of washing, the aim of enhancing the viscosity of an aqueous solution cannot be achieved due to poor solubility of the CMC-H in water; if CMC-Li is used alone as an additive in the water washing process, excessive Li is introduced to inhibit the dissolution of residual alkali on the surface of the material in water. According to the invention, the CMC-X solution is used for washing the high-nickel anode material calcined material, and the CMC-Li ionization can provide extra Li, so that the first effect is improved, and the internal resistance is reduced; CMC-H can react with LiOH and Li under certain conditions 2 CO 3 Reacting to generate carboxymethyl cellulose lithium salt (CMC-Li); based on the characteristics of CMC-X, the viscosity of the aqueous solution can be effectively regulated and controlled through different addition amounts, the washed damage degree of the surface structure of the high-nickel anode material in the water washing process is reduced, and the slow reaction can be carried out with the residual alkali on the surface of the high-nickel anode material, so that the purpose of removing the residual alkali on the surface of the material is achieved. Therefore, the effect of improving circulation and increasing capacity can be achieved by adding carboxymethyl cellulose lithium salt (CMC-Li). In some preferred embodiments of the invention, the molar ratio of CMC-H to CMC-Li is (0.1 to 10): 1, preferably (0.2 to 5): 1.
in the invention, the chemical general formula of the high-nickel anode material-fired material is as follows: li 1+y (Ni a Co b M c B d ) 1-y O 2 Wherein y is more than or equal to 0 and less than or equal to 0.05, a is more than or equal to 0.7 and less than or equal to 0.95, B is more than or equal to 0.01 and less than or equal to 0.2, c is more than or equal to 0 and less than or equal to 0.2, d is more than or equal to 0 and less than or equal to 0.05, a, B, c, d and d=1, M is Mn, al or a combination of the two in any proportion, B is Zn, B, c, d and d 2+ 、Mg 2+ 、Al 3+ 、Y 3+ 、Cr 3+ 、Sc 3+ 、Ga 3+ 、La 3+ 、Sm 3+ 、Ti 4+ 、Zr 4+ 、Nb 5+ 、W 6+ One or a combination of two or more of them. ObtainingThe high-nickel anode material sintering method comprises the following steps: uniformly mixing a high-nickel positive electrode material precursor, a lithium source and an additive, and sintering and crushing to obtain a high-nickel positive electrode material primary sintering material; in the step, the lithium source is lithium hydroxide; the molar ratio of the high-nickel cathode material precursor to lithium in the lithium source is 1: (1.01-1.1); the sintering temperature is 700-900 ℃, the sintering time is 8-24 h, and the sintering atmosphere is oxygen.
In the invention, the step of obtaining the CMC-X solution of carboxymethyl cellulose comprises the following steps:
s21, dispersing CMC-Na into an ethanol solution, adding dilute hydrochloric acid, mixing, reacting, performing suction filtration, washing, drying and crushing to obtain CMC-H; in the process, the molar ratio of HCl to CMC-Na is more than 1, and further ranges from 1.05 to 1.5:1, and further 1.1:1; the reaction temperature is 30-40 ℃ and the reaction time is 1-3 h. In some embodiments of the invention, the volume fraction of the ethanol solution is 10% to 98%, further 50% to 95%, further 85% to 95%; the dosage ratio of the CMC-Na to the ethanol solution is 1g: (0.5 to 10) ml, further 1g: (2-3) ml, further 1g; the concentration of the dilute hydrochloric acid is 1-12 mol/L, further 3-10 mol/L, further 6mol/L; the dosage ratio of CMC-Na to dilute hydrochloric acid is 1g: (0.1-2) ml; further 1g: (0.5 to 1) ml, further 1g: (0.7-0.8) ml.
S22, dispersing CMC-H into an ethanol solution, adding a LiOH solution for mixing reaction, adjusting the pH of the solution to 6-8, and filtering, washing and drying to obtain CMC-X; in the process, the molar ratio of LiOH to CMC-H is 0.01-1.5, further 0.2-1.0, and further 0.5-0.8; the reaction temperature is 40-60 ℃, and the reaction time is 1-3 h; in the process of adjusting the pH, the selected acid is at least one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid and oxalic acid; in some embodiments of the invention, the volume fraction of the ethanol solution is 10% to 98%, further 50% to 95%, further 85% to 95%; the dosage ratio of the CMC-H to the ethanol solution is 1g: (0.5 to 10) ml, further 1g: (2-3) ml; the concentration of the lithium hydroxide solution is 1-6 mol/L, further 3-5 mol/L, and further 4mol/L; the dosage ratio of CMC-H to lithium hydroxide solution is 1g: (0.1-1) ml; further 1g: (0.3-0.8) ml, further 1g: (0.5-0.7) ml.
The CMC-X is a mixture of the CMC-H and the CMC-Li by the reaction of the CMC-Na, so that the step of separation and purification is directly omitted, the difficulty of synthesis is greatly reduced, and the synthesis of the CMC-X can avoid the introduction of an impurity element Na.
In the invention, the step of obtaining the carboxymethyl cellulose CMC-X solution further comprises the following steps:
s23, dissolving CMC-X in water to obtain a carboxymethyl cellulose CMC-X solution; in the obtained carboxymethyl cellulose CMC-X solution, the mass fraction of CMC-X is 0.1% -10%, further 2% -8%, and further 4%; within this range, the resulting high nickel cathode material has optimal performance.
In the invention, in the washing process, the dosage ratio of the high-nickel anode material calcined material to the carboxymethyl cellulose CMC-X solution is 1g: (0.3-10) ml, further 1g: (0.5-5) ml, further 1g; the temperature of water washing is 10-60 ℃, and further 30-50 ℃; the time is 5-30 min, and further 10-20 min; the water washing is carried out under the condition of stirring, and the stirring speed is 300-500 r/min; the solid-liquid separation mode can be suction filtration or filter pressing; the drying temperature is 80-140 ℃ and the drying time is 6-24 h.
In the invention, the method for removing residual alkali by water washing of the high-nickel anode material further comprises the step of uniformly mixing the dried material and the coating agent and then sintering to obtain the high-nickel anode material.
In the present invention, the kind of the coating agent is not limited, and those skilled in the art can select the coating agent according to actual needs. For example, the capping agent may be an oxide or hydroxide of B, al, mg, V, ti, P, si. The adding amount of the coating agent is 0.05wt% -5 wt% of the total amount of the high-nickel anode material calcined material. In the process, the sintering temperature is 200-600 ℃, and the time is 6-24 h.
The second aspect of the invention provides a high nickel cathode material, which is obtained by the method for removing residual alkali by water washing of the high nickel cathode material provided by the first aspect of the invention.
In the following examples and comparative examples of the present invention, the high nickel cathode material-fired material and carboxymethyl cellulose CMC-X were prepared as follows, unless otherwise specified.
Obtaining a high-nickel anode material first sintering material:
4.0Kg of Ni 0.85 Co 0.15 (OH) 2 With 1.88Kg of lithium hydroxide, 44.9gAl 2 O 3 Uniformly mixing in a high-speed mixer, sintering for 10 hours at 730 ℃ in an oxygen atmosphere, and crushing to obtain the high-nickel positive electrode material calcined material.
Synthesis of carboxymethyl cellulose CMC-X:
pouring 500mL of 95% alcohol solution by volume fraction into a 1L glass reaction bottle, adding 200g of CMC-Na, stirring uniformly, slowly adding 150mL of hydrochloric acid (HCl: CMC-Na = 1.1) with the concentration of 6mol/L while stirring, maintaining the reaction temperature at 35 ℃, reacting for 2H, after the reaction is finished, carrying out suction filtration, washing for 2 times by using 85% alcohol, finally drying at 105 ℃, and crushing to obtain CMC-H;
dispersing 154g of CMC-H into 400mL of 90% volume fraction alcoholic solution, adding 100mL of 4mol/L LiOH solution (LiOH: CMC-H = 4.
Example 1
Adding 10g of CMC-X into 500ml of deionized water, uniformly stirring, and maintaining the water temperature at 30 ℃; adding 500g of high-nickel anode material calcined material into the solution, stirring at the speed of 400r/min for 10min, and separating the material and water by adopting suction filtration; drying the materials at 120 ℃ for 10 hours; mixing 300g of the dried material with 1.72g of boric acid, and coating for 6h at 250 deg.C to obtain the nickelic material NCM-2% CMC.
Example 2
Adding 20g of CMC-X into 500ml of deionized water, uniformly stirring, and maintaining the water temperature at 30 ℃; adding 500g of high-nickel anode material calcined material into the solution, stirring at the speed of 400r/min for 10min, and separating the material and water by adopting suction filtration; drying the material at 120 deg.C for 10h to obtain water-washed and dried high nickel material NCM-4% CMC-HG.
Example 3
Adding 20g of CMC-X into 500ml of deionized water, uniformly stirring, and maintaining the water temperature at 30 ℃; adding 500g of high-nickel anode material calcined material into the solution, stirring at the speed of 400r/min for 10min, and separating the material and water by adopting suction filtration; drying the materials at 120 ℃ for 10 hours; mixing 300g of the dried material with 1.72g of boric acid, and coating for 6h at 250 ℃ to obtain the high nickel material NCM-4 percent CMC.
Example 4
Adding 30g of CMC-X into 500ml of deionized water, uniformly stirring, and maintaining the water temperature at 30 ℃; adding 500g of high-nickel anode material calcined material into the solution, stirring at the speed of 400r/min for 10min, and separating the material and water by adopting suction filtration; drying the materials at 120 ℃ for 10 hours; mixing 300g of the dried material with 1.72g of boric acid, and coating for 6h at 250 ℃ to obtain the high nickel material NCM-6% CMC.
Example 5
Adding 40g of CMC-X into 500ml of deionized water, uniformly stirring, and maintaining the water temperature at 30 ℃; adding 500g of high-nickel anode material calcined material into the solution, stirring at the speed of 400r/min for 10min, and separating the material and water by adopting suction filtration; drying the materials at 120 ℃ for 10 hours; mixing 300g of the dried material with 1.72g of boric acid, and coating for 6h at 250 deg.C to obtain the nickelic material NCM-8% CMC.
Comparative example 1
Taking 500ml of deionized water, and keeping the water temperature at 30 ℃ under the condition of stirring; adding 500g of high-nickel anode material calcined material into deionized water, stirring at the speed of 400r/min for 10min, and separating the material and water by adopting suction filtration; drying the material at 120 deg.C for 10h to obtain water-washed dried high nickel material NCM-0% CMC-HG.
Comparative example 2
Taking 500ml of deionized water, and keeping the water temperature at 30 ℃ under the condition of stirring; adding 500g of high-nickel anode material calcined material into deionized water, stirring at the speed of 400r/min for 10min, and separating the material and water by adopting suction filtration; drying the materials at 120 ℃ for 10 hours; mixing 300g of the dried material with 1.72g of boric acid, and coating for 6h at 250 deg.C to obtain the nickelic material NCM-0% CMC.
Test group
The high nickel positive electrode materials obtained in the above examples 1 to 5 and comparative examples 1 to 2 were subjected to performance tests, and the results are shown in fig. 1 to 3 and table 1; wherein, the electrical property test conditions are as follows: the weight ratio of the cathode material to the anode material was 97.2: 1.3 (PVDF): 1.5 (SP) and spreading the aluminum foil on a coater to coat the aluminum foil (the areal density is 15.0-17.0 mg/cm) 2 ) Drying in 80 deg.C blast drying oven for 2 hr; then punching, weighing, baking the pole piece and manufacturing into a CR2032 button cell; and finally, placing the battery into a blue light test system for electrical performance test. The electrical property test parameters are set as: the voltage range was 2.5V-4.25V,0.2C/0.2C → 0.2C/1C → 0.2C/1C → 0.5C/0.1C, and the test results are shown in Table 1.
TABLE 1
Figure BDA0003418611520000091
Fig. 1 is an SEM image of the high nickel cathode materials obtained in comparative example 1 and example 2 of the present invention. As can be seen from fig. 1, the material pores on the surface of the sample obtained by conventional water washing (comparative example 1) are larger, while the pores on the surface of the sample obtained by water washing of example 2 according to the present invention are smaller, which indicates that the washing strength of the material surface during the water washing process according to the present invention is relatively weak.
Fig. 2 is a charge and discharge graph of a high nickel cathode material obtained by using one sintered material according to the present invention and comparative example 2 and example 3. As can be seen from fig. 2, the 0.2C discharge capacity of the high nickel cathode material synthesized by the water washing method of embodiment 3 of the present invention is higher than that of the material synthesized by the conventional water washing method, because the trace amount of CMC-Li remaining on the surface after the water washing of the present invention can play a role in inhibiting the Li ion precipitation and supplementing lithium of the internal structure of the high nickel cathode material during the drying and secondary firing processes. As can be seen by combining the data in Table 1, the surface residual alkali content of the material synthesized by the method of the present invention is not much different from the surface residual alkali content of the material synthesized by the conventional method.
FIG. 3 is a graph showing cycle characteristics of the high nickel positive electrode materials obtained in comparative examples 1 to 2 and examples 2 to 3 of the present invention. In fig. 3, by comparing comparative example 1 and example 2, the cycle performance of the water-washed sample of the present invention is superior to that of the conventional water-washed sample (comparative example 1), indicating that the water-washing process of the present invention causes less damage to the surface structure of the material; by comparing the comparison result of the comparison 2 with the comparison result of the comparison example 3, the cycle performance of the high-nickel cathode material synthesized by the water washing method is obviously improved.
From the results in table 1, it can be seen that, compared with the conventional washing method, the discharge capacity and the first efficiency of the high-nickel cathode material synthesized by the washing method are improved and the cycle performance of the material is also significantly improved under the condition of different addition amounts of CMC-X, wherein the overall performance of the high-nickel cathode material synthesized by adding 4% of CMC-X by washing is optimal.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.

Claims (9)

1. A method for removing residual alkali of a high-nickel cathode material by water washing is characterized by comprising the following steps:
obtaining a first sintering material of the high-nickel anode material;
obtaining a carboxymethyl cellulose CMC-X solution; wherein the CMC-X is that the molar ratio of CMC-H to CMC-Li is (0.1-10): 1;
and washing the high-nickel anode material calcined material by the carboxymethyl cellulose CMC-X solution, and performing solid-liquid separation and drying to obtain a dried material.
2. The method for removing residual alkali by water washing of the high-nickel cathode material according to claim 1, wherein the chemical general formula of the high-nickel cathode material-calcined material is: li 1+y (Ni a Co b M c B d ) 1-y O 2 Wherein y is more than or equal to 0 and less than or equal to 0.05, a is more than or equal to 0.7 and less than or equal to 0.95, b is more than or equal to 0.01 and less than or equal to 0.2, c is more than or equal to 0 and less than or equal to 0.2, d is more than or equal to 0 and less than or equal to 0.05, a, b, c, d and 1 are formed by the following steps ofMn, al or the combination of the two in any proportion, B is Zn 2+ 、Mg 2+ 、Al 3+ 、Y 3+ 、Cr 3+ 、Sc 3+ 、Ga 3+ 、La 3+ 、Sm 3+ 、Ti 4+ 、Zr 4+ 、Nb 5+ 、W 6+ Or a combination of two or more thereof.
3. The method for removing residual alkali by water washing of the high-nickel cathode material according to claim 2, wherein the step of obtaining the high-nickel cathode material calcined material comprises: uniformly mixing a high-nickel anode material precursor, a lithium source and an additive, sintering and crushing to obtain a high-nickel anode material primary sintering material; the lithium source is lithium hydroxide; the molar ratio of the high-nickel cathode material precursor to lithium in the lithium source is 1: (1.01-1.1); the sintering temperature is 700-900 ℃, the sintering time is 8-24 h, and the sintering atmosphere is oxygen.
4. The method for removing residual alkali by water washing of the high-nickel cathode material according to claim 1, wherein the step of obtaining the carboxymethyl cellulose CMC-X solution comprises:
dispersing CMC-Na into an ethanol solution, then adding dilute hydrochloric acid for mixing reaction, and obtaining CMC-H through suction filtration, washing, drying and crushing;
dispersing CMC-H into an ethanol solution, then adding a LiOH solution for mixing reaction, then adjusting the pH of the solution to 6-8, and obtaining the CMC-X through filtering, washing and drying.
5. The method for removing the residual alkali by washing the high-nickel cathode material with water according to claim 4, wherein the molar ratio of HCl to CMC-Na is more than 1, the temperature of the mixed reaction of the CMC-Na and the dilute hydrochloric acid is 30-40 ℃, and the time is 1-3 h; the molar ratio of LiOH to CMC-H is 0.01-1.5, the temperature of the mixing reaction of CMC-H and lithium hydroxide is 40-60 ℃, and the time is 1-3H.
6. The method for removing residual alkali by water washing of the high-nickel cathode material according to claim 5, wherein the step of obtaining the CMC-X solution of carboxymethyl cellulose further comprises:
dissolving CMC-X in water to obtain a carboxymethyl cellulose CMC-X solution; in the obtained carboxymethyl cellulose CMC-X solution, the mass fraction of CMC-X is 0.1 percent to 10 percent.
7. The method for removing residual alkali by washing the high-nickel cathode material with water according to claim 1, wherein in the washing process, the using amount ratio of the high-nickel cathode material-calcined material to the carboxymethyl cellulose CMC-X solution is 1g: (0.3-10) ml, and the temperature of water washing is 10-60 ℃.
8. The method for removing the residual alkali by washing the high-nickel cathode material with water according to claim 1, further comprising uniformly mixing the dried material and the coating agent and then sintering the mixture to obtain the high-nickel cathode material.
9. A high nickel positive electrode material, which is obtained by the method of removing residual alkali by washing the high nickel positive electrode material according to any one of claims 1 to 8.
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