COBALT-FREE SYSTEM, POSITIVE ELECTRODE SLURRY, SLURRY HOMOGENIZATION METHOD THEREFOR, AND USE THEREOF

Abstract

Provided are a cobalt-free system, a positive electrode slurry, a slurry homogenization method therefor, and the use thereof. The cobalt-free system comprises a cobalt-free material, a binder, a conductive agent and a pH regulator. The cobalt-free system can reduce the rebound degree of the viscosity of a slurry after leaving to stand to the same degree as that of a ternary 811 single crystal, and can also improve the stability of the coating surface density of the cobalt-free material to the same level as that of a ternary material.

Claims

1. A cobalt-free system, comprising a cobalt-free material, a binder, a conductive agent and a pH adjusting agent.

2. The cobalt-free system according to claim 1, wherein the cobalt-free material is Li.sub.xNi.sub.yMn.sub.zO.sub.2, wherein x is 1 to 1.1, y is 0.5 to 0.8, z is 0.2 to 0.5, and y+z=1.

3. The cobalt-free system according to claim 2, wherein the cobalt-free material is Li.sub.xNi.sub.0.75Mn.sub.0.25O.sub.2, wherein x is 1 to 1.1.

4. The cobalt-free system according to claim 1, wherein the binder is polyvinylidene fluoride with a number average molecular weight of 0.5-1.5 million.

5. The cobalt-free system according to claim 1, wherein the binder is added in an amount of 1-1.8 parts by weight based on the cobalt-free material added in an amount of 95.4-97.8 parts by weight.

6. The cobalt-free system according to claim 1, wherein the conductive agent comprises a combination of a first conductive agent and a second conductive agent, wherein the first conductive agent is conductive carbon black and the second conductive agent is a single-wall carbon nanotube.

7. The cobalt-free system according to claim 6, wherein the first conductive agent is added in an amount of 1-2 parts by weight and the second conductive agent is added in an amount of 0.2-0.8 parts by weight based on the cobalt-free material added in an amount of 95.4-97.8 parts by weight.

8. The cobalt-free system according to claim 1, wherein the pH adjusting agent comprises oxalic acid and/or maleic acid.

9. The cobalt-free system according to claim 1, wherein the pH adjusting agent is added in an amount of 0.1-0.5% by mass of total dry powder in the cobalt-free material, the binder and the conductive agent.

10. A positive electrode slurry, comprising a colloidal solution and the cobalt-free system according to claim 1, wherein the cobalt-free system is dispersed in the colloidal solution.

11. The positive electrode slurry according to claim 10, wherein a method for preparing the colloidal solution comprises carrying out glue making on a binder A and a solvent to obtain the colloidal solution.

12. The positive electrode slurry according to claim 11, wherein the glue making is carried out in a glue making machine for 200-300 min.

13. The positive electrode slurry according to claim 11, the binder A is polyvinylidene fluoride with a number average molecular weight of 0.5-1.5 million.

14. The positive electrode slurry according to claim 11, wherein the solvent comprises any one selected from the group consisting of N-methylpyrrolidone, N,N-dimethylformamide, dimethylsulfoxide, and a combination of at least two selected therefrom.

15. The positive electrode slurry according to claim 11, wherein the binder A is added in an amount of 5-20 parts by weight based on the solvent added in an amount of 80-95 parts by weight.

16. A slurry homogenization method of the positive electrode slurry according to claim 10, comprising: adding and dispersing a cobalt-free system in a colloidal solution to obtain the positive electrode slurry.

17. The slurry homogenization method according to claim 16, comprising the following steps: (1) a binder, a first conductive agent and a pH adjusting agent in a cobalt-free system are added to a colloidal solution and mixed to obtain a conductive glue A; (2) a second conductive agent in the cobalt-free system is added to the conductive glue A obtained in step (1) and mixed to obtain a conductive glue B; and (3) a cobalt-free material in the cobalt-free system is added to the conductive glue B obtained in step (2) and mixed to obtain the positive electrode slurry.

18. The slurry homogenization method according to claim 17, wherein in step (1), the mixing is carried out through stirring which has a linear speed of 15-16 m/s and lasts for 40-80 min; wherein in step (2), the mixing is carried out through stirring which has a linear speed of 15-16 m/s and lasts for 40-80 min; and wherein in step (3), the mixing is carried out through stirring which has a linear speed of 19-20 m/s and lasts for 100-140 min.

19. (canceled)

20. (canceled)

21. A positive electrode pole piece, comprising a positive electrode current collector and a slurry layer on an outer surface of the positive electrode current collector, wherein the slurry layer uses the positive electrode slurry according to claim 10.

22. A lithium-ion battery, comprising a positive electrode pole piece, a negative electrode pole piece and a separator, wherein the positive electrode pole piece is the positive electrode pole piece according to claim 21.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0035] The drawings are used to provide a further understanding of technical solutions of the present disclosure, constitute a part of the description, explain the technical solutions of the present disclosure in conjunction with embodiments of the present application and do not limit the technical solutions of the present disclosure.

[0036] FIG. 1 shows curves of the viscosity of slurries varying with a shear rate, which are obtained in Example 1 and Comparative Example 2 of the present disclosure.

DETAILED DESCRIPTION

[0037] In an embodiment, the present disclosure provides a cobalt-free system. The cobalt-free system includes a cobalt-free material, a binder, a conductive agent and a pH adjusting agent. The cobalt-free material is Li.sub.xNi.sub.yMn.sub.zO.sub.2, where x is 1 to 1.1, y is 0.5 to 0.8, z is 0.2 to 0.5, and y+z=1.

[0038] The cobalt-free system of the present disclosure can reduce the degree to which the viscosity of a slurry rebounds after standing. In some embodiments, the viscosity of the slurry before standing is 5260-6980 cp and the viscosity of the slurry after 12 h of standing rebounds to 12120-14950 cp so that the slurry reaches the same degree as a ternary 811 single crystal. Meanwhile, the cobalt-free system can improve the stability in the surface density of coating of the cobalt-free material. The surface density of coating fluctuates by as low as ±1.03% so that the cobalt-free material reaches the same level as a ternary material.

[0039] In an embodiment, the cobalt-free material is prepared by a method which includes steps described below.

[0040] In S100, a precursor Ni.sub.yMn.sub.z(OH).sub.2, a lithium source LiOH and a dopant are mixed under a stirring condition at a rate of 600-1000 rpm such as 600 rpm, 700 rpm, 800 rpm, 900 rpm or 1000 rpm for 10-40 min such as 10 min, 15 min, 20 min, 25 min, 30 min or 40 min, so that a mixture is obtained.

[0041] In an embodiment, a doping element in the dopant is selected from any one or a combination of at least two of Ti, Zr or Al, the dopant is doped in an amount of 2000-5000 ppm such as 2000 ppm, 2500 ppm, 3000 ppm, 4000 ppm, 4500 ppm or 5000 ppm, and a ratio of Li to a transition metal in the dopant is 1.04-1.06, such as 1.04, 1.05 or 1.06.

[0042] In S200, the mixture obtained in step S100 is subjected to primary calcination at an oxygen concentration of 90-100 vol %, where in the process of primary calcination, the temperature is raised to 930-950° C. at a rate of 1-4° C./min and then maintained for 5-15 h so that a material after primary calcination is obtained.

[0043] In S300, the material after primary calcination, which is obtained in step S200, is pulverized and ground by a roller and sieved by a 325 mesh sieve so that a sieved material is obtained.

[0044] In S400, the sieved material obtained in step S300 is subjected to dry coating, where nano Zr and Al oxides (where the content of Zr is 0.1% to 0.3 wt % and the content of Al is 0.1% to 0.2 wt %) are mixed with the sieved material for 10-30 min such as 10 min, 15 min, 20 min or 30 min at a high temperature and at a rotational speed of 800-1200 rpm such as 800 rpm, 850 rpm, 900 rpm, 1000 rpm, 1100 rpm or 1200 rpm so that a coated material is obtained.

[0045] In S500, the coated material obtained in step S400 is subjected to secondary calcination, where the temperature is raised to 400-700° C. at a rate of 2-4° C./min and maintained for 5-8 h so that a material after secondary calcination is obtained.

[0046] In S600, the material after secondary calcination, which is obtained in step S500, is sieved by a 325 mesh sieve or a 350 mesh sieve so that the cobalt-free material is obtained.

[0047] All the cobalt-free materials LiNi.sub.0.75Mn.sub.0.25O.sub.2, LiNi.sub.0.8Mn.sub.0.2O.sub.2 and LiNi.sub.0.5Mn.sub.0.5O.sub.2 may be prepared by the preceding preparation method. Using LiNi.sub.0.8Mn.sub.0.2O.sub.2 as an example, in an embodiment, a method for preparing LiNi.sub.0.8Mn.sub.0.2O.sub.2 includes steps described below.

[0048] In S100, a precursor Ni.sub.0.8Mn.sub.0.2(OH).sub.2, a lithium source LiOH and a dopant (any one or a combination of at least two of Ti, Zr or Al, the dopant being doped in an amount of 5000 ppm, and a ratio of Li to a transition metal in the dopant being 1.06) are mixed under a stirring condition at a rate of 1000 rpm for 10 min so that a mixture is obtained.

[0049] In S200, the mixture obtained in step S100 is subjected to primary calcination at an oxygen concentration of 90%, where in the process of primary calcination, the temperature is raised to 950° C. at a rate of 2° C./min and then maintained for 12 h so that a material after primary calcination is obtained.

[0050] In S300, the material after primary calcination, which is obtained in step S200, is pulverized and ground by a roller and sieved by a 325 mesh sieve so that a sieved material is obtained.

[0051] In S400, the sieved material obtained in step S300 is subjected to dry coating, where nano Zr and Al oxides (where the content of Zr is 0.2 wt % and the content of Al is 0.1 wt %) are mixed with the sieved material for 15 min at a high temperature and at a rotational speed of 1000 rpm so that a coated material is obtained.

[0052] In S500, the coated material obtained in step S400 is subjected to secondary calcination, where the temperature is raised to 500° C. at a rate of 3° C./min and maintained for 6 h so that a material after secondary calcination is obtained.

[0053] In S600, the material after secondary calcination, which is obtained in step S500, is sieved by a 325 mesh sieve so that the cobalt-free material is obtained.

Example 1

[0054] This example provides a cobalt-free system, which includes 96.5 parts by weight of a cobalt-free material, 1.5 parts by weight of a binder, 1.5 parts by weight of a first conductive agent, 0.5 parts by weight of a second conductive agent and a pH adjusting agent (added in an amount of 0.3% by mass of dry powder in the cobalt-free material, the binder, the first conductive agent and the second conductive agent), where the cobalt-free material is LiNi.sub.0.75Mn.sub.0.25O.sub.2, the binder is polyvinylidene fluoride with a number average molecular weight of 1 million, the conductive agent includes the first conductive agent and the second conductive agent, the first conductive agent is conductive carbon black, the second conductive agent is a single-wall carbon nanotube, and the pH adjusting agent is oxalic acid.

[0055] This example provides a positive electrode slurry, which includes a colloidal solution and the preceding cobalt-free system dispersed in the colloidal solution. A method for preparing the colloidal solution includes carrying out glue making on 90 parts by weight of N-methylpyrrolidone and 10 parts by weight of polyvinylidene fluoride with a number average molecular weight of 1 million in a glue making machine for 240 min to obtain the colloidal solution.

[0056] This example provides a slurry homogenization method of the positive electrode slurry, which includes steps described below.

[0057] (1) The binder, the first conductive agent and the pH adjusting agent in the cobalt-free system were added to the colloidal solution and mixed in a stirrer so that a conductive glue A was obtained, where the mixture was stirred at a linear speed of 15.7 m/s for 60 min.

[0058] (2) The second conductive agent in the cobalt-free system was added to the conductive glue A obtained in step (1) and mixed in the stirrer so that a conductive glue B was obtained, where the mixture was stirred at a linear speed of 15.7 m/s for 60 min.

[0059] (3) The cobalt-free material in the cobalt-free system was added to the conductive glue B obtained in step (2) and mixed in the stirrer so that the positive electrode slurry was obtained, where the mixture was stirred at a linear speed of 19.7 m/s for 120 min.

[0060] The viscosity of the slurry obtained in this example was tested. It was found that the viscosity of the slurry was 5660 cp and rebounded to 13000 cp after 12 h of standing. It can be seen that the viscosity of the slurry rebounds to a relatively small degree after 12 h of standing.

[0061] The slurry obtained in this example was coated on a positive electrode pole piece. A long pole piece with a length of 1 m was taken and samples were taken once every 20 cm and taken eight times so that 48 pieces of data were obtained in total. The surface density of coating was calculated based on the 48 pieces of data and fluctuated by ±1.03%. The fluctuation in surface density (SD) was calculated by the following formula:

[00001]$\mathrm{SD}=\frac{\mathrm{MAX}\left(S_{\mathrm{MAX}}-S_{\mathrm{AVE}},S_{\mathrm{AVE}}-S_{\mathrm{MIN}}\right)}{S_{\mathrm{AVE}}}\times 100\%;$

where S.sub.MAX denotes a maximum value of the surface density of coating, S.sub.AVE denotes an average value of the surface density of coating, S.sub.MIN denotes a minimum value of the surface density of coating, and MAX(S.sub.MAX-S.sub.AVE, S.sub.AVE-S.sub.MIN) demotes a larger value between a difference between the maximum value and the average value and a difference between the average value and the minimum value.

Example 2

[0062] This example provides a cobalt-free system, which includes 95.4 parts by weight of a cobalt-free material, 1.8 parts by weight of a binder, 2 parts by weight of a first conductive agent, 0.8 parts by weight of a second conductive agent and a pH adjusting agent (added in an amount of 0.1% by mass of dry powder in the cobalt-free material, the binder, the first conductive agent and the second conductive agent), where the cobalt-free material is Li.sub.1.1Ni.sub.0.8Mn.sub.0.2O.sub.2, the binder is polyvinylidene fluoride with a number average molecular weight of 0.5 million, the conductive agent includes the first conductive agent and the second conductive agent, the first conductive agent is conductive carbon black, the second conductive agent is a single-wall carbon nanotube, and the pH adjusting agent is maleic acid.

[0063] This example provides a positive electrode slurry, which includes a colloidal solution and the preceding cobalt-free system dispersed in the colloidal solution. A method for preparing the colloidal solution includes carrying out glue making on 95 parts by weight of N-methylpyrrolidone and 5 parts by weight of polyvinylidene fluoride with a number average molecular weight of 0.5 million in a glue making machine for 200 min to obtain the colloidal solution.

[0064] This example provides a slurry homogenization method of the positive electrode slurry, which includes steps described below.

[0065] (1) The binder, the first conductive agent and the pH adjusting agent in the cobalt-free system were added to the colloidal solution and mixed in a stirrer so that a conductive glue A was obtained, where the mixture was stirred at a linear speed of 15 m/s for 80 min.

[0066] (2) The second conductive agent in the cobalt-free system was added to the conductive glue A obtained in step (1) and mixed in the stirrer so that a conductive glue B was obtained, where the mixture was stirred at a linear speed of 15 m/s for 80 min.

[0067] (3) The cobalt-free material in the cobalt-free system was added to the conductive glue B obtained in step (2) and mixed in the stirrer so that the positive electrode slurry was obtained, where the mixture was stirred at a linear speed of 19 m/s for 140 min.

[0068] The viscosity of the slurry obtained in this example was tested. It was found that the viscosity of the slurry was 5260 cp and rebounded to 12770 cp after 12 h of standing. It can be seen that the viscosity of the slurry rebounds to a relatively small degree after 12 h of standing.

[0069] The method for testing the surface density of coating in Example 1 was used for this example. It was found that the surface density of coating fluctuated by ±1.05%.

Example 3

[0070] This example provides a cobalt-free system, which includes 97.8 parts by weight of a cobalt-free material, 1 part by weight of a binder, 1 part by weight of a first conductive agent, 0.2 parts by weight of a second conductive agent and a pH adjusting agent (added in an amount of 0.5% by mass of dry powder in the cobalt-free material, the binder, the first conductive agent and the second conductive agent), where the cobalt-free material is LiNi.sub.0.5Mn.sub.0.5O.sub.2, the binder is polyvinylidene fluoride with a number average molecular weight of 1.5 million, the conductive agent includes the first conductive agent and the second conductive agent, the first conductive agent is conductive carbon black, the second conductive agent is a single-wall carbon nanotube, and the pH adjusting agent is oxalic acid.

[0071] This example provides a positive electrode slurry, which includes a colloidal solution and the preceding cobalt-free system dispersed in the colloidal solution. A method for preparing the colloidal solution includes carrying out glue making on 80 parts by weight of N-methylpyrrolidone and 20 parts by weight of polyvinylidene fluoride with a number average molecular weight of 1.5 million in a glue making machine for 300 min to obtain the colloidal solution.

[0072] This example provides a slurry homogenization method of the positive electrode slurry, which includes steps described below.

[0073] (1) The binder, the first conductive agent and the pH adjusting agent in the cobalt-free system were added to the colloidal solution and mixed in a stirrer so that a conductive glue A was obtained, where the mixture was stirred at a linear speed of 16 m/s for 40 min.

[0074] (2) The second conductive agent in the cobalt-free system was added to the conductive glue A obtained in step (1) and mixed in the stirrer so that a conductive glue B was obtained, where the mixture was stirred at a linear speed of 16 m/s for 40 min.

[0075] (3) The cobalt-free material in the cobalt-free system was added to the conductive glue B obtained in step (2) and mixed in the stirrer so that the positive electrode slurry was obtained, where the mixture was stirred at a linear speed of 20 m/s for 100 min.

[0076] The viscosity of the slurry obtained in this example was tested. It was found that the viscosity of the slurry was 6640 cp and rebounded to 12120 cp after 12 h of standing. It can be seen that the viscosity of the slurry rebounds to a relatively small degree after 12 h of standing.

[0077] The method for testing the surface density of coating in Example 1 was used for this example. It was found that the surface density of coating fluctuated by ±1.306%.

Example 4

[0078] This example differs from Example 1 only in that the conductive agent in the cobalt-free system was only the first conductive agent, and other components and the preparation methods were the same as those of Example 1.

[0079] The viscosity of the slurry obtained in this example was tested. It was found that the viscosity of the slurry was 6230 cp and rebounded to 12130 cp after 12 h of standing. It can be seen that the viscosity of the slurry rebounds to a relatively small degree after 12 h of standing.

[0080] The method for testing the surface density of coating in Example 1 was used for this example. It was found that the surface density of coating fluctuated by ±1.446%.

[0081] As can be seen from the comparison of Example 1 and Example 4, when the cobalt-free system includes only the first conductive agent, the surface density of coating fluctuates to a relatively large degree.

Example 5

[0082] This example differs from Example 1 only in that the conductive agent was only the second conductive agent, and other components and the preparation methods were the same as those of Example 1.

[0083] The viscosity of the slurry obtained in this example was tested. It was found that the viscosity of the slurry was 6210 cp and rebounded to 13250 cp after 12 h of standing. It can be seen that the viscosity of the slurry rebounds to a relatively small degree after 12 h of standing.

[0084] The method for testing the surface density of coating in Example 1 was used for this example. It was found that the surface density of coating fluctuated by ±1.485%.

[0085] As can be seen from the comparison of Example 1 and Example 5, when the cobalt-free system includes only the second conductive agent, the surface density of coating fluctuates to a relatively large degree.

Example 6

[0086] This example differs from Example 1 only in that the single-wall carbon nanotube in the cobalt-free system was replaced with a carbon nanotube, and other components and the preparation methods were the same as those of Example 1.

[0087] The viscosity of the slurry obtained in this example was tested. It was found that the viscosity of the slurry was 6980 cp and rebounded to 13260 cp after 12 h of standing. It can be seen that the viscosity of the slurry rebounds to a relatively small degree after 12 h of standing.

[0088] The method for testing the surface density of coating in Example 1 was used for this example. It was found that the surface density of coating fluctuated by ±1.37%.

[0089] As can be seen from the comparison of Example 1 and Example 6, when the single-wall carbon nanotube is replaced with the carbon nanotube, the surface density of coating fluctuates to a relatively large degree.

Example 7

[0090] This example differs from Example 1 only in that the binder, polyvinylidene fluoride, had a number average molecular weight of 5 million, and other components and the preparation methods were the same as those of Example 1.

[0091] The viscosity of the slurry obtained in this example was tested. It was found that the viscosity of the slurry was 6350 cp and rebounded to 14950 cp after 12 h of standing. It can be seen that the viscosity of the slurry rebounds to a relatively small degree after 12 h of standing.

[0092] The method for testing the surface density of coating in Example 1 was used for this example. It was found that the surface density of coating fluctuated by ±1.32%.

[0093] As can be seen from the comparison of Example 1 and Example 7, when polyvinylidene fluoride with a high molecular weight is used as the binder, the viscosity of the slurry rebounds to a relatively small degree and the surface density of coating fluctuates to a relatively large degree.

Comparative Example 1

[0094] This example differs from Example 1 only in that the cobalt-free system included no pH adjusting agent, oxalic acid, and other components and the preparation methods were the same as those of Example 1.

[0095] The viscosity of the slurry obtained in this comparative example was tested. It was found that the viscosity of the slurry was 5630 cp and rebounded to 47000 cp after 12 h of standing. It can be seen that the viscosity of the slurry rebounds to a relatively large degree after 12 h of standing.

[0096] The method for testing the surface density of coating in Example 1 was used for this comparative example. It was found that the surface density of coating fluctuated by ±2.02%.

[0097] As can be seen from the comparison of Example 1 and Comparative Example 1, when the cobalt-free system includes no oxalic acid, the viscosity of the slurry rebounds to a relatively large degree and the surface density of coating fluctuates to a relatively large degree, which is not conducive to a practical application.

Comparative Example 2

[0098] This comparative example provides a slurry homogenization method, which includes steps described below.

[0099] (1) 6.25 parts by weight of polyvinylidene fluoride (with a number average molecular weight of 0.8 million) and 93.75 parts by weight of N-methylpyrrolidone were added to a glue making machine and subjected to glue making for 240 min so that a colloidal solution was obtained.

[0100] (2) 1.2 parts by weight of polyvinylidene fluoride (with a number average molecular weight of 0.8 million) and 0.7 parts by weight of carbon nanotubes were added to a stirrer and stirred so that a conductive glue 1 was obtained.

[0101] (3) 1.8 parts by weight of conductive carbon black and the conductive glue 1 obtained in step (2) were added to the stirrer and stirred so that a conductive glue 2 was obtained.

[0102] (4) 96.3 parts by weight of a cobalt-free material and the conductive glue 2 obtained in step (3) were added to the stirrer and stirred so that a slurry was obtained.

[0103] The viscosity of the slurry obtained in this comparative example was tested. It was found that the viscosity of the slurry was 6850 cp and rebounded to 70000 cp after 12 h of standing. It can be seen that the viscosity of the slurry rebounds to a relatively large degree after 12 h of standing.

[0104] The method for testing the surface density of coating in Example 1 was used for this comparative example. It was found that the surface density of coating fluctuated by ±2.28%.

[0105] As can be seen from the comparison of Example 1 and Comparative Example 2, when the slurry homogenization method of a ternary system is used, the viscosity of the obtained slurry rebounds to a relatively large degree and the surface density of coating fluctuates to a relatively large degree, which is not conducive to a practical application.

[0106] FIG. 1 shows curves of the viscosity of slurries obtained in Example 1 and Comparative Example 2 varying with a shear rate at different rotational speeds (a rotational speed from 0 r/min to 300 r/min and a rotational speed from 300 r/min to 0 r/min). As can be seen from FIG. 1, in Comparative Example 2, when the rotational speed changes from 0 r/min to 300 r/min, the viscosity of the slurry is 133000 cp at 1 r/min, and when the rotational speed changes from 300 r/min to 0 r/min, the viscosity of the slurry is 10901 cp at 1 r/min; in Example 1, when the rotational speed changes from 0 r/min to 300 r/min, the viscosity of the slurry is 24544 cp at 1 r/min, and when the rotational speed changes from 300 r/min to 0 r/min, the viscosity of the slurry is 12311 cp at 1 r/min. As can be seen from the comparison of Comparative Example 2 and Example 1, when the rotational speed changes from 300 r/min to 0 r/min, the viscosity of the slurry in Example 1 significantly decreases at 1 r/min and the area of a thixotropic ring (that is, an area between two viscosity curves for 0-300 r/min and 300-0 r/min) significantly decreases, which indicates that the slurry in Example 1 has stronger fluidity and a stronger ability to recover to an initial state and is more conducive to coating leveling. It indicates that the use of the cobalt-free system in Example 1 for slurry homogenization has a significant optimization and improvement effect.