A kind of method of phenolic resin cladding tertiary cathode material
阅读说明：本技术 一种酚醛树脂包覆三元正极材料的方法 (A kind of method of phenolic resin cladding tertiary cathode material ) 是由 严雪枫 丁楚雄 李道聪 夏昕 于 2019-08-22 设计创作，主要内容包括：本发明涉及一种酚醛树脂包覆三元正极材料的方法,将三元正极材料、酚醛树脂和分散剂的混合物进行球磨后干燥；本发明通过将分散剂、酚醛树脂以及三元正极材料的混合物通过球磨的方式来达到酚醛树脂对三元正极材料的包覆,该方法简单易行,能使酚醛树脂对三元正极材料紧密结合且均匀的包覆,使得酚醛树脂的包覆性能更好,进而达到不仅可以提高活性物质的循环性能,可以更好地利用酚醛树脂的电化学性能,改善三元正极材料的电化学性能。(The present invention relates to a kind of methods of phenolic resin cladding tertiary cathode material, will be dry after the mixture progress ball milling of tertiary cathode material, phenolic resin and dispersing agent；The present invention by the mixture of dispersing agent, phenolic resin and tertiary cathode material by ball milling by way of reach phenolic resin to the cladding of tertiary cathode material, this method is simple and easy, phenolic resin can be made to combine closely tertiary cathode material and uniformly coated, so that the covering property of phenolic resin is more preferable, and then reach the cycle performance that active material not only can be improved, the chemical property that phenolic resin can preferably be utilized, improves the chemical property of tertiary cathode material.)
1. a kind of method of phenolic resin cladding tertiary cathode material, it is characterised in that: by tertiary cathode material, phenolic resin and The mixture of dispersing agent carries out drying after ball milling.
2. a kind of method of phenolic resin cladding tertiary cathode material according to claim 1, it is characterised in that: described The mass ratio of tertiary cathode material, phenolic resin and dispersing agent is 8-12:0.5-1.5:9-13.
3. a kind of method of phenolic resin cladding tertiary cathode material according to claim 1, it is characterised in that: described three First positive electrode is prepared as follows to obtain: in protective atmosphere, by NiSO4、CoSO4And MnSO4Aqueous solution be added In stirred tank reactor, Hybrid Heating stirring, while alkaline solution is added, the pH value of solution is controlled, after stirring 12 h, will be obtained Material filtered, dried after, be mixed together with lithium source, under the conditions of air or oxygen, sintering tertiary cathode material is prepared Material.
4. a kind of method of phenolic resin cladding tertiary cathode material according to claim 3, it is characterised in that: described NiSO4、CoSO4And MnSO4Ion molar ratio be Ni:Co:Mn=6:2:2.
5. a kind of method of phenolic resin cladding tertiary cathode material according to claim 3, it is characterised in that: described Alkaline solution is the NaOH solution and ammonium hydroxide of 2 mol/L of concentration, and the pH value for controlling solution is 11-12.
6. a kind of method of phenolic resin cladding tertiary cathode material according to claim 3, it is characterised in that: the guarantor Protecting atmosphere is inert gas or nitrogen.
7. a kind of method of phenolic resin cladding tertiary cathode material according to claim 3, it is characterised in that: the burning The condition of knot is 700-750 DEG C, 10-15h.
8. a kind of method of phenolic resin cladding tertiary cathode material according to claim 1, it is characterised in that: described Phenolic resin the preparation method is as follows: phenol, aniline, toluene are mixed and heated to 50 DEG C of stirrings, add formaldehyde, deionized water And catalyst in aniline, it is warming up to 95 DEG C and reacts 50 minutes, cooling and dewatering, the product obtained after dehydration is dissolved in ethyl alcohol, and is added ZnCl2, stirring to ethyl alcohol is all after volatilization, and constant temperature keeps 24 h at 400 DEG C, obtains phenolic resin.
9. a kind of method of phenolic resin cladding tertiary cathode material according to claim 8, it is characterised in that: described ZnCl2Mass ratio with product is 2-5:1.
10. a kind of method of phenolic resin cladding tertiary cathode material according to claim 1, it is characterised in that: described Drying be spray drying, the parameter of spray drying are as follows: 280-300 DEG C of inlet temperature, outlet temperature be 110-120 DEG C, air-flow Amount is 4-6 m3/h。
Technical field
The present invention relates to field of lithium ion battery material more particularly to a kind of sides of phenolic resin cladding tertiary cathode material Method.
Background technique
Based on ternary transition metal oxide (LiNixCoyMnzO2/ NCM) positive electrode be always treated as it is most promising Lithium ion battery material, relative to traditional positive electrode LiCoO2, ternary material has high-energy density, and it is inexpensive, it is low The features such as toxicity.
However, the lower circulation ability of NCM material limits its use under the conditions of high-voltage charging；To solve this Problem, people have attempted various methods to optimize material, including impurity and surface cladding；Wherein, although surface cladding is One simple, economic method, however surface coated thickness is a crucial factor, because most of covering material is electricity Chemical inertness and insulation, when clad too it is thin completely can not coat ternary material when, clad can not prevent that internal Mn's is molten The side reaction of solution and electrode；When clad is too thick, the electric conductivity and lithium ion diffusion velocity of material will affect, to influence The circulation volume and rate capability of material.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of phenolic resin cladding tertiary cathode material.
To achieve the above object, the invention adopts the following technical scheme:
A kind of method of phenolic resin cladding tertiary cathode material, it is characterised in that: by tertiary cathode material, phenolic resin and divide The mixture of powder carries out drying after ball milling.
Preferably, the mass ratio of the tertiary cathode material, phenolic resin and dispersing agent is 8-12:0.5-1.5:9- 13。
Preferably, the tertiary cathode material is prepared as follows to obtain: in protective atmosphere, by NiSO4、 CoSO4And MnSO4Aqueous solution be added in stirred tank reactor, Hybrid Heating stirring while being added alkaline solution, controls solution PH value, stir 12 h after, after obtained material is filtered, dried, be mixed together with lithium source, in air or oxygen condition Under, tertiary cathode material is prepared in sintering.
Preferably, the NiSO4、CoSO4And MnSO4Ion molar ratio be Ni:Co:Mn=6:2:2.
Preferably, the alkaline solution is the NaOH solution and ammonium hydroxide of 2 mol/L of concentration, and the pH value for controlling solution is 11-12。
Preferably, the protective atmosphere is inert gas or nitrogen.
Preferably, the condition of the sintering is 700-750 DEG C, 10-15h.
Preferably, the phenolic resin stirs the preparation method is as follows: phenol, aniline, toluene are mixed and heated to 50 DEG C It mixes, adds formaldehyde, deionized water and catalyst in aniline, be warming up to 95 DEG C and react 50 minutes, cooling and dewatering obtains after dehydration Product is dissolved in ethyl alcohol, and ZnCl is added2, stirring to ethyl alcohol is all after volatilization, and constant temperature keeps 24 h at 400 DEG C, obtains phenolic aldehyde Resin.
Preferably, the ZnCl2Mass ratio with product is 2-5:1.
Preferably, the drying is spray drying, the parameter of spray drying are as follows: 280-300 DEG C of inlet temperature, outlet temperature Degree is 110-120 DEG C, and throughput is 4-6 m3/h。
The beneficial effects of the present invention are:
The present invention by the mixture of dispersing agent, phenolic resin and tertiary cathode material by ball milling by way of reach phenol For urea formaldehyde to the cladding of tertiary cathode material, this method is simple and easy, phenolic resin can be made to combine closely tertiary cathode material And uniform cladding, so that the covering property of phenolic resin is more preferable, and then reach the cyclicity that active material not only can be improved Can, the chemical property of phenolic resin can be preferably utilized, the chemical property of tertiary cathode material is improved.
Detailed description of the invention
Fig. 1 is the capacity circulating figure of embodiment 1, embodiment 2, embodiment 3 and embodiment 5.
Specific embodiment
The present invention will be further described With reference to embodiment:
Following embodiments select NCM622 as tertiary cathode material to be covered, and the preparation method of NCM622 presoma is such as Under: in N2Under the conditions of, it is 2.0 mol L by concentration-1NiSO4, CoSO4And MnSO4(cation mole ratio be Ni:Co:Mn= Aqueous solution 6:2:2) is pumped into continuous stirred tank reactor, while adding the NaOH and ammonium hydroxide of 2 mol/L, is adjusted pH and is existed 11-12 is vigorously stirred 12 h under 60 degree.The material that will then obtain, filtering, is drying to obtain NCM622 presoma.