CN113363431B - Doping modified cathode material with high stability of ion channel - Google Patents

Doping modified cathode material with high stability of ion channel Download PDF

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CN113363431B
CN113363431B CN202110348994.6A CN202110348994A CN113363431B CN 113363431 B CN113363431 B CN 113363431B CN 202110348994 A CN202110348994 A CN 202110348994A CN 113363431 B CN113363431 B CN 113363431B
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nickel cobalt
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lithium
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汉海霞
陈瑶
许梦清
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Wanxiang A123 Systems Asia Co Ltd
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Abstract

The invention relates to the field of lithium battery anode materials, and discloses a doped modified anode material with high stability of an ion channel, aiming at the problem of poor cycle performance of an anode material in the existing lithium battery, wherein the doped modified anode material comprises the following components in parts by weight: the lithium iron manganese phosphate material is mixed in the loaded lithium nickel cobalt manganese oxide, and the mass ratio of the loaded lithium nickel cobalt manganese oxide to the lithium iron manganese phosphate material is 1: 0.25-0.4. The preparation process of the nickel-cobalt-loaded lithium manganate comprises the following steps: (1) manufacturing a three-dimensional arrangement frame; (2) forming a first carrier structure; (3) selective dissolution; (4) grafting an active group; (5) and (4) loading. The method can prepare the cathode material with good thermal conductivity, electrical conductivity, high-stability pore channels and good integrity, so that the prepared cathode material of the lithium battery has stronger cycle performance and longer service life, and can effectively realize material optimization and process optimization of the lithium battery.

Description

Doped modified cathode material with high stability of ion channel
Technical Field
The invention relates to the field of lithium battery anode materials, in particular to a doping modified anode material with high stability of an ion channel.
Background
A lithium ion battery is a secondary battery (rechargeable battery) that mainly operates by movement of lithium ions between a positive electrode and a negative electrode. During charging and discharging, Li ions are intercalated and deintercalated back and forth between two electrodes: during charging, Li ions are extracted from the positive electrode and are inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true during discharge. At present, a plurality of methods for improving the cycle performance in the lithium ion battery are adopted, stable materials including anode and cathode and electrolyte materials are selected and then combined in a most reasonable proportioning mode to form the high-performance lithium ion battery. In most cases, improving the cycling performance of the cell starts with a positive electrode material, such as doping and coating improvement of a lithium ion ternary material (NCM) positive electrode material to slow down the deterioration of the crystal structure of the positive electrode material during cycling. During the use of the battery, due to the continuous insertion and extraction of the Li-ion battery in the battery, the positive electrode material and the negative electrode material are required to have strong physical stability and chemical stability. Physical stability: the positive electrode material and the negative electrode material are required to have stable structures in the conducting process and the charging and discharging process, and not only need to have an ion channel for ensuring smooth migration of Li ions, but also need to have the capability of Li ion de-intercalation for preventing cavity collapse, especially under the condition of high heat generation temperature after the battery is continuously charged and discharged. Chemical stability: when the temperature and the humidity in the battery change, all components of the electrode material still keep a better shape, and Li ion insertion, extraction and transportation are not influenced. Therefore, the preparation of the lithium battery cathode material with high physical stability and chemical stability has important significance.
Patent No. CN2013106975871, patent name: LiV3O8And LiNi0.4Co0.2Mn0.4O2The invention relates to a preparation method of a blending modified lithium battery anode material, in particular to a LiV3O8And LiNi0.4Co0.2Mn0.4O2A preparation method of blending modified lithium battery anode material. The method of the invention comprises the following steps: a. positive electrode material LiV3O8Preparing; b. ternary positive electrode LiNi0.4Co0.2Mn0.4O2Preparing; c. the positive electrode material LiV3O8And LiNi0.4Co0.2Mn0.4O2According to the following steps of 3: 7, mixing in a three-dimensional conical mixer; sintering in a muffle furnace, and presintering for 2h at 480-; sintering at 650-675 ℃ for 4 h; sintering at 800-; then naturally cooling with a furnace, crushing, and finally preparing the blending material (LiV)3O8And LiNi0.4Co0.2Mn0.4O2). The invention uses ternary material and LiV3O8The blending modification can obtain the anode material with high compaction density, and the detection can effectively improve the capacity performance.
The defects of the patent are that only simple physical mixing is adopted, and high-temperature sintering is needed after mixing, so that the matrix structure of the ternary material is easy to damage on one hand, and no chemical bond is generated between mixed components, so that the construction of a lithium ion channel is not facilitated on the other hand.
Disclosure of Invention
The invention aims to overcome the problem of poor cycle performance of the anode material in the lithium battery in the prior art, and provides the doping modified anode material with high stability of an ion channel.
In order to achieve the purpose, the invention adopts the following technical scheme:
a doping modified positive electrode with high stability of an ion channel is prepared from the following materials: and the lithium iron manganese phosphate material is mixed in the loaded lithium nickel cobalt manganese oxide.
Preferably, the mass ratio of the nickel cobalt-supported lithium manganate to the lithium iron manganese phosphate material is 1: 0.25-0.4.
The nickel cobalt-loaded lithium nickel manganese oxide has a stable and ordered ion channel arrangement structure, a plurality of hydroxyl groups and positively charged metal active sites exist on the nickel cobalt-loaded lithium nickel manganese oxide, and a lithium manganese iron phosphate material with an olivine-shaped crystal structure is doped into the nickel cobalt-loaded lithium nickel manganese oxide material, so that the lithium manganese iron phosphate material inherits the stable structure of a lithium iron phosphate olivine crystal, the structural stability of the lithium nickel cobalt-loaded lithium nickel manganese oxide is superior to the layered structure of a ternary material, and the lithium nickel cobalt manganese oxide has unique advantages in the aspect of cycle performance; the lithium iron manganese phosphate material has a relatively stable lithium ion channel, and a coordination structure Mn is arranged around the lithium ion channel2+O6Composition of the structural active site (Mn) on lithium manganese iron phosphate2+、O2-And PO4 3-And the like) can generate an attraction coordination effect with a plurality of hydroxyl groups and positively charged metal active sites on the loaded nickel cobalt lithium manganate to form an effective unified whole, and the lithium manganese iron phosphate can further complicate and diversify the lithium ion pore channel structure on the loaded nickel cobalt lithium manganate to prepare the lithium ion pore channel for crisscross traffic with the advantages of mishap, ordered arrangement, strong integrity and high stability. Can effectively further improve the effective cycle performance and electrochemistry of the lithium batteryThe performance of the lithium battery greatly prolongs the service life of the lithium battery. In addition, due to the metal ion communication effect of the load carrier loaded with the nickel cobalt lithium manganate, the conductive effect of metal ions among all the added components is further enhanced, and meanwhile, the heat dissipation performance of the anode material is improved, so that the finally prepared lithium battery is more durable.
Preferably, the preparation process of the nickel-cobalt-loaded lithium manganate comprises the following steps:
(1) and (3) manufacturing a three-dimensional arrangement frame: mixing MnSO4·4H2Dispersing O in ethanol, and performing ultrasonic treatment for 20-30min to obtain Mn2+Solution, namely uniformly mixing terephthalic acid, vinyl acetate, vinyl terephthalic acid and dimethylacetamide according to a mass ratio to obtain a mixed solution, and then pouring Mn into the mixed solution2+Heating and stirring the solution to obtain a ligand solution, adding a diethylenetriamine solution, heating to 115-120 ℃, stirring for 1.8-2h, and cooling to room temperature to form a three-dimensional arrangement frame;
(2) making a first carrier structure: adding the three-dimensional arrangement frame into a mixed solution of phenyl propylene and peroxyketal, heating to 85-90 ℃, and preserving heat for 16-18h to obtain a first carrier structure;
(3) selective dissolution: adding trisodium aminotriacetate into the first carrier structure, stirring at normal temperature for 70-80min, standing for 0.3-0.5h, centrifuging to collect a product, washing with ethanol for three times, and drying in an oven at 45-50 ℃ overnight to obtain a load carrier structure;
(4) grafting active group: adding the load carrier structure, the glycidyl neodecanoate and the gamma-cyclodextrin into N, N-dimethylformamide according to the mass ratio, stirring and reacting at 65-75 ℃ for 18-22h, filtering and washing to obtain a grafted carrier structure;
(5) loading: and adding the grafted carrier structure into the nickel cobalt lithium manganate, uniformly mixing, continuously adding PVDF 761, stirring for 3-4h, and filtering to obtain the loaded nickel cobalt lithium manganate.
In the process of preparing the nickel cobalt-loaded lithium manganate, the invention comprises the following steps: mn is used in the step (1)2+Polymerizing terephthalic acid, vinyl acetate, vinyl terephthalic acid and dimethylacetamide as a ligand, and addingPerforming crosslinking on diethylenetriamine to form a three-dimensional arrangement frame which is orderly arranged, wherein polyvinyl acetate, terephthalate and vinyl terephthalate in the three-dimensional arrangement frame are embedded into the structure of the three-dimensional arrangement frame as a substituted ligand; after the styrene monomer and the initiator peroxyketal are added in the step (2), polystyrene arranged along the pore direction can be formed in the three-dimensional arrangement frame, and the terephthalate can be simultaneously connected with Zn2+And polystyrene in the pore channels, and bridging polymer chains of adjacent pore channels together to form a frame structure with high stability; trisodium aminotriacetate is added in the step (3) and is used as a complex compound, so that part of organic frameworks close to polystyrene arrangement in the primary carrier structure can be selectively dissolved, on the premise of ensuring the structural stability, the pore diameter in the three-dimensional arrangement framework is larger, the specific surface area is larger, the adsorption capacity on the lithium nickel cobalt manganese oxide is stronger, and the subsequent adsorption and connection of the lithium nickel cobalt manganese oxide are facilitated; the gamma-cyclodextrin is adopted to carry out activation modification on the load carrier structure in the step (4), and the gamma-cyclodextrin has larger ring shape and more hydroxyl groups, so that the gamma-cyclodextrin can be stably connected to the load carrier structure, and the stability of the structure of the load carrier structure is promoted while the active sites of the hydroxyl groups are increased; in the step (5), more hydroxyl sites are formed on the surface of the activated load carrier structure, metal ion groups on the nickel cobalt lithium manganate and active groups on the PVDF 761 binder can be smoothly adsorbed and connected to the hydroxyl groups, and the hydroxyl sites also have a strong adsorption effect on the organic binder with strong polarity, so that the uniform dispersion of the organic binder is facilitated, and an effective and stable integrated structure is formed.
According to the invention, the order of firstly preparing the load carrier structure and then loading the nickel cobalt lithium manganate is adopted for combination, so that the activity of the raw material of the nickel cobalt lithium manganate can be protected to a greater extent, and the situation that the embedded lithium nickel cobalt lithium manganate damages or blocks a lithium ion channel under the action of a polymer or a ligand in the preparation process is avoided. The preparation method of the invention enables the nickel cobalt lithium manganate to be orderly arranged along the frame structure of the load carrier structure, and the load carrier structure can also provide a better supporting effect for the nickel cobalt lithium manganate, and has significant positive effects on the orderly arrangement of lithium ion channels in the nickel cobalt lithium manganate and the prevention of the collapse of the lithium ion channels in the nickel cobalt lithium manganate. In addition, Mn in the load carrier structure can effectively communicate the nickel cobalt lithium manganate in each channel in the load carrier structure frame to form countless densely communicated veins, so that the conductive capability and the heat dissipation capability in the anode material are improved to a greater extent, and the anode material has a longer service cycle.
Preferably, in step (1), MnSO4·4H2The ratio of O to ethanol is 1.2-1.4 g: 80 mL; terephthalic acid, vinyl acetate, vinyl terephthalic acid and dimethylacetamide in a mass ratio of 1: 1.05-1.3: 1.1-1.3: 1.5-1.6.
Preferably, in step (1), Mn is added2+The volume ratio of the solution to the mixed solution to the diethylenetriamine solution is 1: 2.8-3.6: 0.6-0.8.
In the anode doping modified material, the proportion of manganese has a great influence on the cycle performance of the anode doping modified material, and the selection of a proper manganese-iron element proportion is crucial: on one hand, the platform voltage of manganese is about 4.1V, the median voltage of the anode doped modified material can be improved by improving the content of manganese, but the excessive content of manganese has the risk of separating out manganese element, and has great influence on capacity and safety, so that the selection of proper manganese element is most critical2+The stability of the manganese element is further improved by coordination.
Preferably, in step (1), the stirring conditions are: stirring for 0.8-1.2h at 96-100 ℃.
Preferably, in the step (2), the mass ratio of the three-dimensional arrangement framework to the phenylpropene to the peroxyketal is 3: 2-2.5: 0.5-0.8.
Preferably, in step (3), the mass ratio of the first carrier structure to trisodium nitrilotriacetate is 2-2.5: 0.7-1.0.
Preferably, in the step (4), the mass ratio of the load carrier structure and the glycidyl neodecanoate to the gamma-cyclodextrin and the N, N-dimethylformamide is 1: 0.6-0.8: 1.5-2: 0.4-0.6.
Preferably, in the step (5), the ratio of the grafting support structure, the nickel cobalt lithium manganate and the PVDF 761 is 1 g: 2-3 g: 0.15-0.4 g.
Therefore, the invention has the following beneficial effects:
(1) the loaded lithium nickel cobalt manganese oxide is doped with a lithium manganese iron phosphate material with an olivine-shaped crystal structure to form an effective unified whole, the lithium manganese iron phosphate can further complicate and diversify a lithium ion pore channel structure on the loaded lithium nickel cobalt manganese oxide, and a lithium ion pore channel which is well-arranged, orderly arranged, strong in integrity and high in stability and is used for crisscross traffic is prepared;
(2) according to the preparation method, the nickel cobalt lithium manganate can be orderly arranged along the framework structure of the load carrier structure, the load carrier structure can also provide a good supporting effect for the nickel cobalt lithium manganate, and the preparation method has a remarkable positive effect on the orderly arrangement of lithium ion pore channels in the nickel cobalt lithium manganate and the prevention of the collapse of the lithium ion pore channels in the nickel cobalt lithium manganate;
(3) the metal ion (Mn) communication effect of the load carrier of the nickel cobalt lithium manganate further strengthens the conductive effect of metal ions among all the added components, and simultaneously improves the heat dissipation performance of the anode material, so that the finally prepared lithium battery is more durable.
Detailed Description
The invention is further described with reference to specific embodiments.
General examples
A doping modified positive electrode with high stability of an ion channel is prepared from the following materials: the loaded nickel cobalt lithium manganate comprises the following components in a mass ratio of 1:0.25-0.4 of the material is mixed with the lithium iron manganese phosphate.
The preparation process of the load nickel cobalt lithium manganate comprises the following steps:
(1) and (3) manufacturing a three-dimensional arrangement frame: mixing MnSO4·4H2Dispersing O in ethanol, and performing ultrasonic treatment for 20-30min to obtain Mn2+Solution, namely uniformly mixing terephthalic acid, vinyl acetate, vinyl terephthalic acid and dimethylacetamide according to a mass ratio to obtain a mixed solution, and pouring Mn into the mixed solution2+Stirring in the solution at 96-100 deg.C for 0.8-1.2h to obtainAdding a diethylenetriamine solution into the ligand solution, heating to 115-120 ℃, stirring for 1.8-2h, and cooling to room temperature to form a three-dimensional arrangement frame; MnSO4·4H2The ratio of O to ethanol is 1.2-1.4 g: 80 mL; terephthalic acid, vinyl acetate, vinyl terephthalic acid and dimethylacetamide in a mass ratio of 1: 1.05-1.3: 1.1-1.3: 1.5-1.6; mn2+The volume ratio of the solution to the mixed solution to the diethylenetriamine solution is 1: 2.8-3.6: 0.6-0.8;
(2) making a first carrier structure: adding the three-dimensional arrangement frame into a mixed solution of phenyl propylene and peroxyketal, heating to 85-90 ℃, and preserving heat for 16-18h to obtain a first carrier structure; the mass ratio of the three-dimensional arrangement frame to the phenyl propylene to the peroxyketal is 3: 2-2.5: 0.5-0.8;
(3) selective dissolution: adding trisodium aminotriacetate into the first carrier structure, stirring at normal temperature for 70-80min, standing for 0.3-0.5h, centrifuging to collect a product, washing with ethanol for three times, and drying in an oven at 45-50 ℃ overnight to obtain a load carrier structure; mass ratio of the first carrier structure to trisodium aminotriacetate 2-2.5: 0.7-1.0;
(4) grafting active group: adding the load carrier structure, the glycidyl neodecanoate and the gamma-cyclodextrin into N, N-dimethylformamide according to the mass ratio, stirring and reacting at 65-75 ℃ for 18-22h, filtering and washing to obtain a grafted carrier structure; the mass ratio of the load carrier structure to the neodecanoic acid glycidyl ester to the gamma-cyclodextrin and the N, N-dimethylformamide is 1: 0.6-0.8: 1.5-2: 0.4-0.6;
(5) loading: adding the grafted carrier structure into the nickel cobalt lithium manganate, uniformly mixing, continuously adding PVDF 761, stirring for 3-4h, and filtering to obtain loaded nickel cobalt lithium manganate; the proportion of the grafting carrier structure, the nickel cobalt lithium manganate and the PVDF 761 is 1 g: 2-3 g: 0.15-0.4 g.
Example 1
A doping modified positive electrode with high stability of an ion channel is prepared from the following materials: the loaded nickel cobalt lithium manganate comprises the following components in a mass ratio of 1: 0.32 of the lithium iron manganese phosphate material.
The preparation process of the load nickel cobalt lithium manganate comprises the following steps:
(1) and (3) manufacturing a three-dimensional arrangement frame: mixing MnSO4·4H2Dispersing O in ethanol, and performing ultrasonic treatment for 25min to obtain Mn2+Solution, namely uniformly mixing terephthalic acid, vinyl acetate, vinyl terephthalic acid and dimethylacetamide according to a mass ratio to obtain a mixed solution, and pouring Mn into the mixed solution2+Stirring the solution at the temperature of 98 ℃ for 1.0h to obtain a ligand solution, adding a diethylenetriamine solution, heating the solution to 118 ℃, stirring the solution for 1.9h, and cooling the solution to room temperature to form a three-dimensional arrangement frame; MnSO4·4H2The ratio of O to ethanol was 1.3 g: 80 mL; terephthalic acid, vinyl acetate, vinyl terephthalic acid and dimethylacetamide in a mass ratio of 1: 1.2: 1.2: 1.55; mn2+The volume ratio of the solution to the mixed solution to the diethylenetriamine solution is 1: 3.2: 0.7 of the total weight of the mixture;
(2) making a first carrier structure: adding the three-dimensional arrangement frame into a mixed solution of the phenyl propylene and the peroxyketal, heating to 88 ℃, and preserving heat for 17 hours to obtain a first carrier structure; the mass ratio of the three-dimensional arrangement frame to the phenyl propylene to the peroxyketal is 3: 2.3: 0.65;
(3) selective dissolution: adding trisodium aminotriacetate into the first carrier structure, stirring for 75min at normal temperature, standing for 0.4h, centrifuging to collect a product, washing with ethanol for three times, and drying in an oven at 48 ℃ overnight to obtain a load carrier structure; mass ratio of first carrier structure to trisodium nitrilotriacetate 2.3: 0.85;
(4) grafting active group: adding the load carrier structure, the glycidyl neodecanoate and the gamma-cyclodextrin into N, N-dimethylformamide according to the mass ratio, stirring and reacting for 20 hours at 70 ℃, filtering and washing to obtain a grafted carrier structure; the mass ratio of the load carrier structure to the neodecanoic acid glycidyl ester to the gamma-cyclodextrin and the N, N-dimethylformamide is 1: 0.7: 1.8: 0.5;
(5) loading: adding the grafted carrier structure into the nickel cobalt lithium manganate, uniformly mixing, continuously adding PVDF 761, stirring for 3.5h, and filtering to obtain loaded nickel cobalt lithium manganate; the proportion of the grafting carrier structure, the nickel cobalt lithium manganate and the PVDF 761 is 1 g: 2.5 g: 0.32 g.
Example 2
A doping modified positive electrode with high stability of an ion channel is prepared from the following materials: the loaded nickel cobalt lithium manganate comprises the following components in a mass ratio of 1: 0.35 of the lithium iron manganese phosphate material.
The preparation process of the load nickel cobalt lithium manganate comprises the following steps:
(1) and (3) manufacturing a three-dimensional arrangement frame: mixing MnSO4·4H2Dispersing O in ethanol, and performing ultrasonic treatment for 28min to obtain Mn2+Solution, namely uniformly mixing terephthalic acid, vinyl acetate, vinyl terephthalic acid and dimethylacetamide according to a mass ratio to obtain a mixed solution, and pouring Mn into the mixed solution2+Stirring the solution at 97 ℃ for 1.1h to obtain a ligand solution, adding a diethylenetriamine solution, heating the solution to 116 ℃, stirring the solution for 1.95h, and cooling the solution to room temperature to form a three-dimensional arrangement frame; MnSO4·4H2The ratio of O to ethanol was 1.25 g: 80 mL; terephthalic acid, vinyl acetate, vinyl terephthalic acid and dimethylacetamide in a mass ratio of 1: 1.08: 1.15: 1.52; mn2+The volume ratio of the solution to the mixed solution to the diethylenetriamine solution is 1: 2.9: 0.65;
(2) making a first carrier structure: adding the three-dimensional arrangement frame into a mixed solution of the phenyl propylene and the peroxyketal, heating to 86 ℃, and preserving heat for 16.5 hours to obtain a first carrier structure; the mass ratio of the three-dimensional arrangement frame to the phenyl propylene to the peroxyketal is 3: 2.1: 0.55;
(3) selective dissolution: adding trisodium aminotriacetate into the first carrier structure, stirring for 78min at normal temperature, standing for 0.35h, centrifuging to collect a product, washing with ethanol for three times, and drying in an oven at 46 ℃ overnight to obtain a load carrier structure; mass ratio of first carrier structure to trisodium nitrilotriacetate 2.4: 0.8;
(4) grafting active group: adding the load carrier structure, the glycidyl neodecanoate and the gamma-cyclodextrin into N, N-dimethylformamide according to the mass ratio, stirring and reacting at 68 ℃ for 18.5h, filtering and washing to obtain a grafted carrier structure; the mass ratio of the load carrier structure to the neodecanoic acid glycidyl ester to the gamma-cyclodextrin and the N, N-dimethylformamide is 1: 0.65: 1.9: 0.48;
(5) loading: adding the grafted carrier structure into the nickel cobalt lithium manganate, uniformly mixing, continuously adding PVDF 761, stirring for 3.8 hours, and filtering to obtain loaded nickel cobalt lithium manganate; the proportion of the grafting carrier structure, the nickel cobalt lithium manganate and the PVDF 761 is 1 g: 2.2 g: 0.2 g.
Example 3
A doping modified positive electrode with high stability of an ion channel is prepared from the following materials: the loaded nickel cobalt lithium manganate comprises the following components in a mass ratio of 1: 0.3 mixing and doping the lithium iron manganese phosphate material.
The preparation process of the load nickel cobalt lithium manganate comprises the following steps:
(1) and (3) manufacturing a three-dimensional arrangement frame: mixing MnSO4·4H2Dispersing O in ethanol, and performing ultrasonic treatment for 22min to obtain Mn2+Solution, namely uniformly mixing terephthalic acid, vinyl acetate, vinyl terephthalic acid and dimethylacetamide according to a mass ratio to obtain a mixed solution, and pouring Mn into the mixed solution2+Stirring the solution at 99 ℃ for 0.9h to obtain a ligand solution, adding a diethylenetriamine solution, heating the solution to 119 ℃, stirring the solution for 1.85h, and cooling the solution to room temperature to form a three-dimensional arrangement frame; MnSO4·4H2The ratio of O to ethanol was 1.25 g: 80 mL; terephthalic acid, vinyl acetate, vinyl terephthalic acid and dimethylacetamide in a mass ratio of 1: 1.25: 1.28: 1.58; mn2+The volume ratio of the solution to the mixed solution to the diethylenetriamine solution is 1: 3.4: 0.75;
(2) making a first carrier structure: adding the three-dimensional arrangement frame into a mixed solution of the phenyl propylene and the peroxyketal, heating to 89 ℃, and preserving heat for 16.5 hours to obtain a first carrier structure; the mass ratio of the three-dimensional arrangement frame to the phenyl propylene to the peroxyketal is 3: 2.4: 0.58;
(3) selective dissolution: adding trisodium aminotriacetate into the first carrier structure, stirring for 78min at normal temperature, standing for 0.45h, centrifuging to collect a product, washing with ethanol for three times, and drying in a 58 ℃ oven overnight to obtain a load carrier structure; mass ratio of first carrier structure to trisodium nitrilotriacetate 2.4: 0.95;
(4) grafting active group: adding the load carrier structure, the glycidyl neodecanoate and the gamma-cyclodextrin into N, N-dimethylformamide according to the mass ratio, stirring and reacting at 72 ℃ for 21.5h, filtering and washing to obtain a grafted carrier structure; the mass ratio of the load carrier structure to the neodecanoic acid glycidyl ester to the gamma-cyclodextrin and the N, N-dimethylformamide is 1: 0.75: 1.85: 0.55;
(5) loading: adding the grafted carrier structure into the nickel cobalt lithium manganate, uniformly mixing, continuously adding PVDF 761, stirring for 3.8 hours, and filtering to obtain loaded nickel cobalt lithium manganate; the proportion of the grafting carrier structure, the nickel cobalt lithium manganate and the PVDF 761 is 1 g: 2.8 g: 0.38 g.
Example 4
A doping modified positive electrode with high stability of an ion channel is prepared from the following materials: the loaded nickel cobalt lithium manganate is prepared by the following steps of 1:0.25 of the material is mixed with the lithium iron manganese phosphate.
The preparation process of the load nickel cobalt lithium manganate comprises the following steps:
(1) and (3) manufacturing a three-dimensional arrangement frame: mixing MnSO4·4H2Dispersing O in ethanol, and performing ultrasonic treatment for 30min to obtain Mn2+Solution, namely uniformly mixing terephthalic acid, vinyl acetate, vinyl terephthalic acid and dimethylacetamide according to a mass ratio to obtain a mixed solution, and pouring Mn into the mixed solution2+Stirring the solution at 96 ℃ for 1.2h to obtain a ligand solution, adding a diethylenetriamine solution, heating the solution to 115 ℃, stirring the solution for 2h, and cooling the solution to room temperature to form a three-dimensional arrangement frame; MnSO4·4H2The ratio of O to ethanol was 1.2 g: 80 mL; terephthalic acid, vinyl acetate, vinyl terephthalic acid and dimethylacetamide in a mass ratio of 1: 1.05: 1.3: 1.5; mn2+The volume ratio of the solution to the mixed solution to the diethylenetriamine solution is 1: 2.8: 0.6;
(2) making a first carrier structure: adding the three-dimensional arrangement frame into a mixed solution of the phenyl propylene and the peroxyketal, heating to 85 ℃, and preserving heat for 18 hours to obtain a first carrier structure; the mass ratio of the three-dimensional arrangement frame to the phenyl propylene to the peroxyketal is 3: 2: 0.8;
(3) selective dissolution: adding trisodium aminotriacetate into the first carrier structure, stirring for 70min at normal temperature, standing for 0.5h, centrifuging to collect a product, washing with ethanol for three times, and drying in an oven at 45 ℃ overnight to obtain a load carrier structure; mass ratio of first carrier structure to trisodium nitrilotriacetate 2: 1.0;
(4) grafting active group: adding the load carrier structure, the glycidyl neodecanoate and the gamma-cyclodextrin into N, N-dimethylformamide according to the mass ratio, stirring and reacting for 18 hours at 65 ℃, filtering and washing to obtain a grafted carrier structure; the mass ratio of the load carrier structure to the neodecanoic acid glycidyl ester to the gamma-cyclodextrin and the N, N-dimethylformamide is 1: 0.6: 2: 0.4;
(5) loading: adding the grafted carrier structure into the nickel cobalt lithium manganate, uniformly mixing, continuously adding PVDF 761, stirring for 3h, and filtering to obtain loaded nickel cobalt lithium manganate; the proportion of the grafting carrier structure, the nickel cobalt lithium manganate and the PVDF 761 is 1 g: 2 g: 0.4 g.
Example 5
A doping modified positive electrode with high stability of an ion channel is prepared from the following materials: the loaded nickel cobalt lithium manganate comprises the following components in a mass ratio of 1: 0.4 mixing and doping the lithium iron manganese phosphate material.
The preparation process of the load nickel cobalt lithium manganate comprises the following steps:
(1) and (3) manufacturing a three-dimensional arrangement frame: mixing MnSO4·4H2Dispersing O in ethanol, and performing ultrasonic treatment for 30min to obtain Mn2+Solution, namely uniformly mixing terephthalic acid, vinyl acetate, vinyl terephthalic acid and dimethylacetamide according to a mass ratio to obtain a mixed solution, and pouring Mn into the mixed solution2+Stirring the solution at 100 ℃ for 0.8h to obtain a ligand solution, adding a diethylenetriamine solution, heating the solution to 120 ℃, stirring the solution for 1.8h, and cooling the solution to room temperature to form a three-dimensional arrangement frame; MnSO4·4H2The ratio of O to ethanol was 1.4 g: 80 mL; terephthalic acid, vinyl acetate, vinyl terephthalic acid and dimethylacetamide in a mass ratio of 1: 1.3: 1.1: 1.6; mn2+The volume ratio of the solution to the mixed solution to the diethylenetriamine solution is 1: 3.6: 0.6;
(2) making a first carrier structure: adding the three-dimensional arrangement frame into a mixed solution of the phenyl propylene and the peroxyketal, heating to 90 ℃, and preserving heat for 16 hours to obtain a first carrier structure; the mass ratio of the three-dimensional arrangement frame to the phenyl propylene to the peroxyketal is 3: 2.5: 0.5;
(3) selective dissolution: adding trisodium aminotriacetate into the first carrier structure, stirring for 80min at normal temperature, standing for 0.3h, centrifuging to collect a product, washing with ethanol for three times, and drying in a 50 ℃ oven overnight to obtain a load carrier structure; mass ratio of first support structure to trisodium aminotriacetate 2.5: 0.7;
(4) grafting active group: adding the load carrier structure, the glycidyl neodecanoate and the gamma-cyclodextrin into N, N-dimethylformamide according to the mass ratio, stirring and reacting for 18h at 75 ℃, filtering and washing to obtain a grafted carrier structure; the mass ratio of the load carrier structure to the neodecanoic acid glycidyl ester to the gamma-cyclodextrin and the N, N-dimethylformamide is 1: 0.8: 1.5: 0.6;
(5) loading: adding the grafted carrier structure into the nickel cobalt lithium manganate, uniformly mixing, continuously adding PVDF 761, stirring for 4 hours, and filtering to obtain loaded nickel cobalt lithium manganate; the proportion of the grafting carrier structure, the nickel cobalt lithium manganate and the PVDF 761 is 1 g: 3 g: 0.15 g.
The difference between the comparative example 1 and the example 1 is that the content of the lithium iron manganese phosphate material is too much, and the mass ratio of the lithium nickel cobalt manganese oxide loaded to the lithium iron manganese phosphate material is 1: 0.6, the rest of the procedure was the same as in example 1.
Comparative example 2 differs from example 1 in that the lithium nickel cobalt manganese oxide material was not loaded and the remaining steps were the same as in example 1.
Comparative example 3 differs from example 1 in that Zn (NO) is used in step (1) of the preparation of nickel cobalt-supported lithium manganate3)2·6H2O substituted for MnSO4·4H2O, the remaining steps are the same as in example 1.
Comparative example 4 differs from example 1 in that the selective dissolution in step (3) is omitted from the preparation of the supported lithium nickel cobalt manganese oxide, and the rest of the steps are the same as those in example 1.
The difference between the comparative example 5 and the example 1 is that the grafting active group in the step (4) is omitted in the preparation process of the supported nickel cobalt lithium manganate, and the rest steps are the same as the example 1.
The doped modified cathode materials prepared in the above examples and comparative examples are used to prepare corresponding batteries, and the batteries are tested for relevant performance.
2032 button cell test:
and (3) positive electrode: the anode material comprises Super P, VGCF and PVDF, and the mass ratio of the Super P, the VGCF and the PVDF is 92:2:2: 3;
negative electrode: a metallic lithium plate;
electrolyte solution: 1mol/L LiPF6 was dissolved in Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) (EC: EMC: DMC 1:1:1 wt%);
testing voltage: 2.8-4.3V;
capacity test conditions: and (3) testing constant current charge and discharge at room temperature of 0.1 ℃.
Table 1 items and related performance evaluation indexes of battery prepared by doping modified cathode material
Material Reversible capacity (mAh/g) First efficiency (%) 100-week cycle maintenance (%)
Example 1 177 92 99
Example 2 175 90 98
Example 3 172 91 95
Example 4 169 90 94
Example 5 168 90 97
Comparative example 1 165 88 88
Comparative example 2 147 75 75
Comparative example 3 160 91 86
Comparative example 4 158 90 87
Comparative example 5 162 89 84
Conclusion analysis: it can be seen from the above table that the additive components and related performance parameters of examples 1-5 in the protection range of the present invention can be used to prepare high-stability doped modified cathode materials, and can be used to prepare cathode materials with good thermal conductivity, electrical conductivity, high-stability channels and good integrity, so that the prepared cathode materials of lithium batteries have strong cycle performance and long service life.
The difference between the comparative example 1 and the example 1 is that the content of the lithium iron manganese phosphate material is too much, and the mass ratio of the lithium nickel cobalt manganese oxide loaded to the lithium iron manganese phosphate material is 1: 0.6; because the content of the lithium iron manganese phosphate is excessive, the manganese element is separated out if the content of the manganese element is excessive, the capacity and the safety are greatly influenced, and meanwhile, the content of the nickel-cobalt lithium manganate loaded can be reduced firstly, the stability and the orderliness of an ion pore channel in the doped modified positive electrode material are reduced, and further the performance of the finally prepared battery is reduced.
The difference between the comparative example 2 and the example 1 is that the nickel cobalt lithium manganate material is not loaded; the preparation method of the invention enables the nickel cobalt lithium manganate to be orderly arranged along the frame structure of the load carrier structure, the load carrier structure can also provide better supporting effect for the nickel cobalt lithium manganate, the load carrier structure has obvious positive effect on the orderly arrangement of lithium ion pore channels in the nickel cobalt lithium manganate and the prevention of the collapse of the lithium ion pore channels in the nickel cobalt lithium manganate, and the electric conductivity and the cycle performance of the final material are directly influenced without loading.
Comparative example 3 differs from example 1 in that Zn (NO) is used in step (1) of the preparation of nickel cobalt-supported lithium manganate3)2·6H2O substituted for MnSO4·4H2O; mn in the load carrier structure can effectively communicate the nickel cobalt lithium manganate in each channel in the load carrier structure frame to form countless densely communicated veins, so that the median voltage and the electrical property in the anode material are improved to a greater extent, and the anode material has a longer service cycle; mn of Supported Carrier2+The stability of the manganese element is further improved in coordination, the manganese element precipitation in the anode material is reduced, and the effect cannot be achieved after replacement.
The difference between the comparative example 4 and the example 1 is that the selective dissolution in the step (3) is omitted in the preparation process of the supported nickel cobalt lithium manganate; the selective dissolution in the step (3) is omitted in the process of preparing the loaded nickel cobalt lithium manganate; the selective dissolution of part of the organic framework in the primary carrier structure without adding trisodium aminotriacetate can reduce the porosity and the specific surface area in the final load carrier structure, further reduce the load capacity of the load carrier structure, finally greatly reduce the effective load capacity of the nickel cobalt lithium manganate, ensure that the inner diameter of the pore is small, cannot fully contain the nickel cobalt lithium manganate, cannot effectively protect and support the nickel cobalt lithium manganate, and thus the related electrochemical performance is greatly reduced.
The difference between the comparative example 5 and the example 1 is that the grafting active group in the step (4) is omitted in the preparation process of the supported nickel cobalt lithium manganate; the gamma-cyclodextrin grafting activation of the step (4) is omitted in the process of preparing the load carrier structure; the preparation load carrier structure is not subjected to surface activation grafting, so that the number of active sites on the surface of the preparation load carrier structure is reduced, the nickel cobalt lithium manganate cannot be smoothly or stably connected to the load carrier structure, and a large amount of nickel cobalt lithium manganate is removed and dispersed in the use process of the immobilized nickel cobalt lithium manganate, so that the conductive efficiency and the lithium ion channel stability of the immobilized nickel cobalt lithium manganate are reduced.
As can be seen from the data of examples 1 to 5 and comparative examples 1 to 5, the above requirements can be satisfied in all aspects only by the embodiments within the scope of the claims of the present invention. The change of the mixture ratio, the replacement/addition/subtraction of raw materials, the change of the feeding sequence or the modification or change of process parameters can bring corresponding negative effects.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (9)

1. A doping modified anode material with high stability of an ion channel is characterized in that the doping modified anode material is as follows: the preparation method comprises the following steps of mixing a lithium iron manganese phosphate material in the loaded lithium nickel cobalt manganese oxide, wherein the preparation process of the loaded lithium nickel cobalt manganese oxide comprises the following steps:
(1) and (3) manufacturing a three-dimensional arrangement frame: mixing MnSO4·4H2Dispersing O in ethanol, and performing ultrasonic treatment for 20-30min to obtain Mn2+Solution, namely uniformly mixing terephthalic acid, vinyl acetate, vinyl terephthalic acid and dimethylacetamide according to a mass ratio to obtain a mixed solution, and pouring Mn into the mixed solution2+Heating and stirring the solution to obtain a ligand solution, adding a diethylenetriamine solution, heating the solution to 115-120 ℃, stirring the solution for 1.8 to 2 hours, and cooling the solution to room temperature to form a three-dimensional arrangement frame;
(2) making a first carrier structure: adding the three-dimensional arrangement frame into a mixed solution of phenyl propylene and peroxyketal, heating to 85-90 ℃, and preserving heat for 16-18h to obtain a first carrier structure;
(3) selective dissolution: adding trisodium aminotriacetate into the first carrier structure, stirring at normal temperature for 70-80min, standing for 0.3-0.5h, centrifuging to collect a product, washing with ethanol for three times, and drying in an oven at 45-50 ℃ overnight to obtain a load carrier structure;
(4) grafting active group: adding the load carrier structure, the glycidyl neodecanoate and the gamma-cyclodextrin into N, N-dimethylformamide according to the mass ratio, stirring and reacting at 65-75 ℃ for 18-22h, filtering and washing to obtain a grafted carrier structure;
(5) loading: and adding the grafted carrier structure into the nickel cobalt lithium manganate, uniformly mixing, continuously adding PVDF 761, stirring for 3-4h, and filtering to obtain the loaded nickel cobalt lithium manganate.
2. The doping modified cathode material with high stability of an ion channel as claimed in claim 1, wherein the mass ratio of the nickel cobalt lithium manganate-loaded material to the lithium iron manganese phosphate material is 1: 0.25-0.4.
3. The doping-modified cathode material with high stability of ion channel as claimed in claim 1, wherein in step (1), MnSO4·4H2The ratio of O to ethanol is 1.2-1.4 g: 80 mL; terephthalic acid, vinyl acetate, vinyl terephthalic acid and dimethylacetamide in a mass ratio of 1: 1.05-1.3: 1.1-1.3: 1.5-1.6.
4. The doping-modified cathode material with high stability of ion channel as claimed in claim 1, wherein in step (1), Mn is added2+The volume ratio of the solution to the mixed solution to the diethylenetriamine solution is 1: 2.8-3.6: 0.6-0.8.
5. The doping modified anode material with high ion channel stability as claimed in claim 1, wherein in the step (1), the heating and stirring conditions are as follows: stirring for 0.8-1.2h at 96-100 ℃.
6. The doped modified cathode material with high stability of ion channels as claimed in claim 1, wherein in the step (2), the mass ratio of the three-dimensional arrangement frame to the phenylpropene to the peroxyketal is 3: 2-2.5: 0.5-0.8.
7. The doping-modified cathode material with high ion channel stability as claimed in claim 1, wherein in step (3), the mass ratio of the first support structure to trisodium nitrilotriacetate is 2-2.5: 0.7-1.0.
8. The doped modified cathode material with high ion channel stability as claimed in claim 1, wherein in the step (4), the mass ratio of the load carrier structure, the glycidyl neodecanoate to the gamma-cyclodextrin and the N, N-dimethylformamide is 1: 0.6-0.8: 1.5-2: 0.4-0.6.
9. The doping modified cathode material with high stability of ion channel as claimed in claim 1, wherein in step (5), the ratio of the grafting support structure, nickel cobalt lithium manganate and PVDF 761 is 1 g: 2-3 g: 0.15-0.4 g.
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