CN113346087B - Hybrid phosphate open framework material composite high-nickel positive electrode material and preparation method thereof - Google Patents

Hybrid phosphate open framework material composite high-nickel positive electrode material and preparation method thereof Download PDF

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CN113346087B
CN113346087B CN202110647090.3A CN202110647090A CN113346087B CN 113346087 B CN113346087 B CN 113346087B CN 202110647090 A CN202110647090 A CN 202110647090A CN 113346087 B CN113346087 B CN 113346087B
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open framework
hybrid phosphate
phosphate open
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CN113346087A (en
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张宝
邓鹏�
林可博
丁瑶
邓梦轩
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Zhejiang Power New Energy Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a hybrid phosphate open frame material composite high-nickel anode material, wherein the hybrid phosphate open frame material in the composite material is uniformly coated on the surface of the high-nickel anode material. Also discloses a preparation method of the material, which comprises the following steps: phosphoric acid, oxalic acid and V 2 O 5 Dissolving the mixture and alkali metal hydroxide in deionized water, and carrying out hydrothermal reaction to obtain a hybrid phosphate open framework material; modifying the hybrid phosphate open framework material; dispersing the modified hybrid phosphate open framework material in a non-aqueous solvent, adding a high-nickel anode material, and continuously stirring to enable the modified hybrid phosphate open framework material to be coated on the surface of the high-nickel anode material, thereby obtaining the hybrid phosphate open framework material. The composite cathode material disclosed by the invention can isolate the contact between the high-nickel cathode material and the electrolyte, reduce the occurrence of side reactions, increase the local specific surface area, improve the wettability of the electrolyte, increase the reactive sites, improve the diffusion kinetics of lithium ions and improve the stability and lithium storage performance of the cathode material.

Description

Hybrid phosphate open framework material composite high-nickel cathode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion battery manufacturing, and particularly relates to a hybrid phosphate open framework material composite high-nickel cathode material and a preparation method thereof.
Background
The lithium ion battery as a novel energy storage device has the advantages of high energy density, excellent cycle performance, environmental protection, safety, no memory effect and the like, and is widely applied to various fields. In order to meet the demand of social development, lithium ion batteries are developing toward high specific energy and high power, which requires high stability and high capacity retention of electrode materials.
As the most promising positive electrode material of lithium ion batteries, nickel cobalt lithium manganate (NCM 622, NCM 811) and nickel cobalt lithium aluminate (NCA 811) are the most studied high nickel materials. High nickel materials incorporating LiCoO 2 And LiNiO 2 Has the advantages that: liCoO 2 Good cycle performance and LiNiO 2 The lithium ion battery anode material has high specific capacity and is most hopeful to be widely applied. However, nickel-rich materials also present a number of problems: although the capacity of the battery increases with the increase of the nickel content, the cycle performance of the battery is also deteriorated, and the high nickel material is easy to react with CO in the air 2 And H 2 O reacts to cause severe flatulence, which results in the reduction of cycle performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a hybrid phosphate open framework material composite high-nickel anode material with high stability and good energy storage performance to improve the stability and storage performance of the nickel anode material in electrolyte, and provides a preparation method of the hybrid phosphate open framework material composite high-nickel anode material with simple process and easy realization.
The purpose of the invention is realized by the following technical scheme:
the hybrid phosphate open framework material is uniformly coated on the surface of the high-nickel anode material, and the molecular formula of the hybrid phosphate open framework material is M x N 2-x [(VO) 2 (HPO 4 ) 2 (C 2 O 4 )]Wherein M and N are selected from alkali metals. The high-nickel cathode material is a high-nickel lithium ion battery cathode material which is conventional in the field.
Preferably, the mass ratio of the modified hybrid phosphate open framework material to the high-nickel cathode material is 0.1-10%;
m and N are selected from K, li and Na, further preferably M is Li or K, and N is K; the thickness of the hybrid phosphate open frame material coating layer on the surface of the high-nickel anode material is 30-80 nm.
A preparation method of a hybrid phosphate open framework material composite high-nickel cathode material comprises the following steps:
(1) Weighing the materials according to the proportion, mixing phosphoric acid, oxalic acid and V 2 O 5 Dissolving MOH and NOH in a certain amount of deionized water, and performing ultrasonic treatment for a certain time to obtain a mixed solution; putting the mixture into a reaction kettle, slowly heating the mixture, keeping the temperature for a certain time, and slowly cooling the mixture to room temperature; washing at room temperature, centrifuging, and drying at low temperature to obtain M x N 2-x [(VO) 2 (HPO 4 ) 2 (C 2 O 4 )]A phosphate open framework material;
(2) Dispersing a certain amount of phosphate open framework material in ethanol/methanol, adding a proper amount of surfactant, continuously stirring for a certain time, centrifuging, and washing with alcohol to obtain modified phosphate M x N 2-x [(VO) 2 (HPO 4 ) 2 (C 2 O 4 )]；
(3) Dispersing the modified MOF in ethanol/methanol/N-methyl pyrrolidone uniformly, adding a certain proportion of high-nickel anode material under stirring, continuously stirring for 1-10 h, and making use of the electrostatic attraction effect to make the modified phosphate M x N 2-x [(VO) 2 (HPO 4 ) 2 (C 2 O 4 )]And (MOF) is uniformly compounded on the high-nickel anode material, and the high-nickel anode material is obtained by suction filtration, washing and drying.
Preferably, in the step (1), the MOH and the NOH are one or more of LiOH/NaOH/KOH, and the total molar concentration of the MOH and the NOH in the mixed solution is 4-10 mol/L.
Preferably, in the step (1), the temperature rise is slow temperature rise, and the temperature rise rate of the slow temperature rise is 1-2 ℃/min, so as to ensure the structural consistency and uniformity of the material in the forming process; the hydrothermal reaction temperature is 100-160 ℃, and the preferable temperature is 120-130 ℃; the reaction time is 20 to 30 hours, and the preferable time is 24 to 26 hours; the low-temperature drying temperature is 40-60 ℃.
Preferably, in step (1), the phosphate M is x N 2-x [(VO) 2 (HPO 4 ) 2 (C 2 O 4 )]The element M is Li/Na/K, the element N is Li/Na/K, more preferably M is K or Li, and N is K.
Preferably, in the step (1), the phosphoric acid, oxalic acid and V are mixed in the mixed solution according to a molar ratio 2 O 5 1-10 (MOH and NOH total amount) of.
Preferably, in the step (2), the surfactant is one or more of cationic surfactants APS (3-aminopropyltriethoxysilane), CTAB (cetyltrimethylammonium bromide) and PDDA (polydiallyldimethylammonium chloride), and more preferably APS.
Preferably, in step (2), the phosphate open frame material is dispersed in a non-aqueous solvent for 1h with stirring time > 12h.
Preferably, in step (2), the MOF material: surfactant (b): 0.1-0.5g of ethanol.
Preferably, in the step (3), the mass ratio of the modified MOF to the high nickel material is 0.1% to 10%.
Preferably, in the step (3), the drying time of the nickel-rich material after composite modification is 1 to 10 hours, preferably 2 to 3 hours.
Compared with the prior art, the invention has the following advantages:
1. in the composite cathode material, the hybrid phosphate open frame material is uniformly coated on the surface of the high-nickel cathode material, so that the contact between the high-nickel cathode material and an electrolyte can be isolated, the occurrence of side reactions can be reduced, the local specific surface area can be increased, the wettability of the electrolyte can be improved, the reactive active sites can be increased, the diffusion kinetics of lithium ions can be improved, and the structure, the electrochemical stability and the lithium storage performance of the cathode material can be improved.
2. According to the invention, the MOF containing Li/Na/K elements is synthesized, the MOF is further subjected to modification treatment of a cationic surfactant, and finally compounded with a high-nickel anode material, and finally, on the premise of not damaging the structure of the anode material as much as possible, a layer of MOF material is uniformly coated on the surface of the MOF material, so that the contact with an electrolyte is isolated, the occurrence of side reactions is reduced, the local specific surface area is increased, the wettability of the electrolyte is improved, the reactive active sites are increased, the diffusion kinetics of lithium ions are improved, and the structure, the electrochemical stability and the lithium storage performance of the anode material are improved.
3. The invention is beneficial to obtaining better effects of enhancing the stability of the material, improving the wettability, the lithium ion diffusion dynamics, the lithium storage performance and other comprehensive performances by optimizing the process steps, parameters and the like, and further obtaining better modification effect.
Drawings
Figure 1 is an XRD pattern of the product of example 1 of the invention.
FIG. 2 is a graph of the cycle performance of the product of example 2 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
Example 1
The preparation method of the hybrid phosphate open framework material composite high-nickel cathode material comprises the following steps:
(1) 5 mmol of phosphoric acid, 2 mmol of oxalic acid and 1 mmol of V are sequentially added into a 50mL hydrothermal kettle 2 O 5 And 5 mmol LiOH, adding 50mL deionized water, and performing ultrasonic treatment for 10 min; placing the mixture into an iron reaction kettle, slowly heating to 120 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 24 hours, placing the reaction kettle in the air, and naturally cooling to room temperature; washing with water at room temperature, centrifuging for 1 time, and drying at 60 deg.C to obtain Li 2 [(VO) 2 (HPO 4 ) 2 (C 2 O 4 )]A phosphate framework material.
(2) Dispersing 0.25g phosphate frame material in 50mL ethanol for 1h, adding 20mL LAPS surfactant, stirring for 12h, centrifuging, and washing with alcohol to obtain the final productObtaining modified phosphate Li 2 [(VO) 2 (HPO 4 ) 2 (C 2 O 4 )]。
(3) 0.2g of modified MOF is uniformly dispersed in ethanol, and 2g of LiNi is added 0.5 Co 0.2 Mn 0.3 O 2 Uniformly compounding modified MOF on high-nickel by using electrostatic attraction, filtering, washing, stirring at 50 ℃, and vacuum drying for 2 hours to obtain hybrid phosphate open-framework composite LiNi 0.5 Co 0.2 Mn 0.3 O 2 A material.
With modified LiNi 0.5 Co 0.2 Mn 0.3 O 2 The method comprises the following steps of taking positive electrode material powder as an active substance, mixing the active substance with Acetylene Black (AB) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder according to the mass ratio of 8. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 14mm by punching, drying for 4h at 105 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and assembling the pole piece into a CR2032 type button cell in the glove box. The battery uses a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and a porous polyethylene film with the diameter of 18mm and the model of Celgard2300 as a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. As shown in FIG. 1, the coated sample was LiNi 0.5 Co 0.2 Mn 0.3 O 2 The material, the coating does not change the crystal structure of the material. The sample was activated at 4.5V for 3 cycles at 0.1C and then cycled for 100 cycles at 3C rate. The specific discharge capacity after 100 cycles is 122.5 mA h g -1 The capacity retention ratio was 84.1%.
Example 2
The preparation method of the hybrid phosphate open framework material composite high-nickel cathode material comprises the following steps:
(1) Sequentially adding 5 mmol of phosphoric acid, 2 mmol of oxalic acid and 1 mmol of V into a 100mL hydrothermal kettle 2 O 5 Adding 5 mmol KOH, adding 50mL deionized water, and performing ultrasonic treatment for 10 min; placing the mixture into an iron reaction kettle, slowly heating to 120 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 24 hours, placing the reaction kettle in the air, and naturally cooling to room temperature; washing with water at room temperature, centrifuging for 1 time, and drying at 60 deg.C. To obtain K 2 [(VO) 2 (HPO 4 ) 2 (C 2 O 4 )]A phosphate framework material.
(2) Dispersing 0.25g of phosphate frame material in 50mL of ethanol for 1h, adding 20mL of APS surfactant, continuously stirring for 12h, centrifuging, and washing with alcohol to obtain modified K 2 [(VO) 2 (HPO 4 ) 2 (C 2 O 4 )]A phosphate salt.
(3) 0.2g of modified MOF is uniformly dispersed in ethanol, and 2g of LiNi is added 0.5 Co 0.2 Mn 0.3 O 2 A material. And the modified MOF is uniformly compounded on the high nickel by utilizing the electrostatic attraction effect. Filtering, washing, stirring at 50 ℃, and vacuum drying for 2h to obtain hybrid phosphate open-framework composite LiNi 0.5 Co 0.2 Mn 0.3 O 2 A material.
The modified NCM523 positive electrode material powder is used as an active substance, mixed with Acetylene Black (AB) serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder in a mass ratio of 8. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 14mm by punching, drying for 4h at 100 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and assembling the pole piece into a CR2032 type button cell in the glove box. The battery uses a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and a porous polyethylene film with the diameter of 18mm and the model of Celgard2300 as a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. As shown in fig. 2, the sample was activated at 4.5V for 3 cycles at 0.1C and then cycled at 3C rate for 100 cycles. The specific discharge capacity after 100 cycles is 146.3 mA h g -1 The 3C capacity retention rate was 97.33%.
Example 3
The preparation method of the hybrid phosphate open framework material composite high-nickel cathode material comprises the following steps:
(1) 5 mmol of phosphoric acid, 2 mmol of oxalic acid and 1 mmol of V are sequentially added into a 100mL hydrothermal kettle 2 O 5 And 5 mmol LiOH, adding 20mL deionized water, and performing ultrasonic treatment for 5 min; placing the mixture into an iron reaction kettle, slowly heating to 140 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 24 hours, placing the reaction kettle in the air, and naturally cooling to room temperature; washing with water at room temperature, centrifuging for 1 time, and drying at 50 deg.C. To obtain Li 2 [(VO) 2 (HPO 4 ) 2 (C 2 O 4 )]A phosphate framework material.
(2) Dispersing 0.2g of phosphate framework material in 50mL of ethanol for 1h, adding 10mL of APS surfactant, continuously stirring for 12h, centrifuging, and washing with alcohol to obtain modified Li 2 [(VO) 2 (HPO 4 ) 2 (C 2 O 4 )]A phosphate salt.
(3) And (3) uniformly dispersing 0.1g of modified MOF in ethanol, adding 1g of NCM811 material, uniformly compounding the modified MOF on high nickel by using the action of electrostatic attraction, carrying out suction filtration and washing, stirring at 60 ℃, and carrying out vacuum drying for 2h to obtain the hybrid phosphate open framework composite NCM811 material.
The modified NCA811 cathode material powder is used as an active substance, mixed with Acetylene Black (AB) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder according to the mass ratio of 8. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 14mm by punching, drying for 4h in the vacuum drying oven at 100 ℃, placing the pole piece in a glove box with the water content and the oxygen content of less than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and then assembling the pole piece into a CR2032 type button cell in the glove box. The battery uses a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and a porous polyethylene film with the diameter of 18mm and the model of Celgard2300 as a diaphragm.
And after the battery is assembled and aged for 12 hours, carrying out charge and discharge tests of different potentials. The sample was activated at 4.5V for 3 cycles at 0.1C and then cycled at 10C for 100 cycles. The specific discharge capacity after 100 cycles is 131.1 mA h g -1 The capacity retention rate was 72.6%.
Example 4
The preparation method of the hybrid phosphate open framework material composite high-nickel cathode material comprises the following steps:
(1) 5 mmol of phosphoric acid, 2 mmol of oxalic acid and 1 mmol of V are sequentially added into a 100mL hydrothermal kettle 2 O 5 And 5 mmol LiOH, adding 20mL deionized water, and performing ultrasonic treatment for 5 min; placing the mixture into an iron reaction kettle, slowly heating to 140 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 24 hours, placing the reaction kettle in the air, and naturally cooling to room temperature; washing with water at room temperature, centrifuging for 1 time, and drying at 50 deg.C. To obtain Li 2 [(VO) 2 (HPO 4 ) 2 (C 2 O 4 )]A phosphate framework material.
(2) Dispersing 0.2g of phosphate frame material in 50mL of ethanol for 1h, adding 10mL of PDDA surfactant, continuously stirring for 12h, centrifuging, and washing with alcohol to obtain modified Li 2 [(VO) 2 (HPO 4 ) 2 (C 2 O 4 )]A phosphate salt.
(3) 0.1g of modified MOF is uniformly dispersed in ethanol, and then 1g of NCM811 material is added, so that the modified MOF is uniformly compounded on high nickel by utilizing the electrostatic attraction effect. And (3) carrying out suction filtration and washing, stirring to dry at 60 ℃, and carrying out vacuum drying for 2h to obtain the hybrid phosphate open framework composite NCM811 material.
Using modified NCA811 anode material powder as an active substance, and mixing the active substance with Acetylene Black (AB) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder according to massMixing according to the ratio of 8. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 14mm by punching, drying for 4h at 100 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and assembling the pole piece into a CR2032 type button cell in the glove box. The battery uses a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and a porous polyethylene film with the diameter of 18mm and the model of Celgard2300 as a diaphragm. After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. The sample was activated at 4.5V for 3 cycles at low rate 0.1C and then cycled for 100 cycles at 10C. The specific discharge capacity after 100 cycles is 103.7 mA h g -1 The capacity retention rate was 68.3%.
Example 5
The preparation method of the hybrid phosphate open framework material composite high-nickel cathode material comprises the following steps:
(1) Sequentially adding 5 mmol of phosphoric acid, 2 mmol of oxalic acid and 1 mmol of V into a 50mL hydrothermal kettle 2 O 5 2.5 mmol LiOH +2.5 mmol KOH, then 20mL deionized water is added, and ultrasonic treatment is carried out for 5 min; placing the mixture into an iron reaction kettle, slowly heating to 120 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 24 hours, placing the reaction kettle in the air, and naturally cooling to room temperature; washing with water at room temperature, centrifuging for 1 time, and drying at 60 deg.C. Thus obtaining LiK [ (VO) 2 (HPO 4 ) 2 (C 2 O 4 )]A phosphate framework material.
(2) Dispersing 0.2g of phosphate frame material in 50mL of ethanol for 1h, adding 5mL of PDDA surfactant, continuously stirring for 12h, centrifuging, and washing with alcohol to obtain modified LiK [ (VO) 2 (HPO 4 ) 2 (C 2 O 4 )]A phosphate salt.
(3) 0.1g of modified MOF was dispersed uniformly in ethanol, and then 5g of NCM622 material was added. And the modified MOF is uniformly compounded on the high nickel by utilizing the electrostatic attraction effect. And (4) carrying out suction filtration and washing, stirring at 50 ℃, and carrying out vacuum drying for 2h to obtain the hybrid phosphate open framework composite NCM622 material.
The modified NCM622 positive electrode material powder is used as an active substance, the active substance is mixed with Acetylene Black (AB) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder according to the mass ratio of 8. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 14mm by punching, drying for 4h at 95 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content both lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and then assembling the pole piece into a CR2032 type button cell in the glove box. The battery uses a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and a porous polyethylene film with the diameter of 18mm and the model of Celgard2300 as a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. The sample was activated at 4.5V for 3 cycles at 0.1C and then cycled for 100 cycles at 3C rate. The specific discharge capacity after 100 cycles is 135.4 mA h g -1 The capacity retention rate was 89.5%.
Example 6
The preparation method of the hybrid phosphate open framework material composite high-nickel cathode material comprises the following steps:
(1) Sequentially adding 5 mmol of phosphoric acid, 2 mmol of oxalic acid and 1 mmol of V into a 50mL hydrothermal kettle 2 O 5 2.5 mmol NaOH +2.5 mmol KOH, then 20mL deionized water is added, and ultrasonic treatment is carried out for 5 min; placing the mixture into an iron reaction kettle, slowly heating to 120 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 24 hours, placing the reaction kettle in the air, and naturally cooling to room temperature; washing with water at room temperature, centrifuging for 1 time, and drying at 60 deg.C. Thus obtaining NaK [ (VO) 2 (HPO 4 ) 2 (C 2 O 4 )]A phosphate framework material.
(2) Dispersing 0.2g of phosphate frame material in 50mL of ethanol for 1hAdding 5mL PDDA surfactant, stirring for 12h, centrifuging, and washing with alcohol to obtain modified NaK [ (VO) 2 (HPO 4 ) 2 (C 2 O 4 )]A phosphate salt.
(3) 0.1g of modified MOF was dispersed uniformly in ethanol, and then 5g of NCM622 material was added. And the modified MOF is uniformly compounded on the high nickel by utilizing the electrostatic attraction effect. And (4) carrying out suction filtration and washing, stirring at 50 ℃, and carrying out vacuum drying for 2h to obtain the hybrid phosphate open framework composite NCM622 material.
The modified NCM622 positive electrode material powder is used as an active substance, the active substance is mixed with Acetylene Black (AB) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder according to the mass ratio of 8. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 14mm by punching, drying for 4h at 95 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and assembling the pole piece into a CR2032 type button cell in the glove box. The battery uses a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and a porous polyethylene film with the diameter of 18mm and the model of Celgard2300 as a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. The sample was activated at 4.5V for 3 cycles at 0.1C and then cycled for 100 cycles at 3C rate. The specific discharge capacity after 100 cycles is 124.5 mA h g -1 The capacity retention rate was 84.2%.
Comparative example 1
The method comprises the steps of taking unmodified NCM622 positive electrode material powder as an active substance, mixing the active substance with Acetylene Black (AB) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder according to the mass ratio of 8. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 14mm by punching, drying for 4h at 95 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content both lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and then assembling the pole piece into a CR2032 type button cell in the glove box. The battery uses a pure metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, and a porous polyethylene film with the diameter of 18mm and the model of Celgard2300 as a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. The sample was activated at 4.5V for 3 cycles at 0.1C and then cycled for 100 cycles at 3C rate. The specific discharge capacity after 100 cycles is 107.4 mA h g -1 The capacity retention rate was 62.5%.
The above description is only a basic description of the present invention, and any equivalent changes made according to the technical solution of the present invention should fall within the protection scope of the present invention.

Claims (7)

1. The hybrid phosphate open framework material composite high-nickel anode material is characterized in that the hybrid phosphate open framework material is uniformly coated on the surface of the high-nickel anode material, and the molecular formula of the hybrid phosphate open framework material is M x N 2-x [(VO) 2 (HPO 4 ) 2 (C 2 O 4 )]M is Li or K, N is K; the thickness of the hybrid phosphate open frame material coating layer on the surface of the high-nickel anode material is 30-80 nm; the preparation method of the hybrid phosphate open framework material composite high-nickel cathode material comprises the following steps:
(1) Phosphoric acid, oxalic acid and V 2 O 5 Dissolving alkali metal hydroxide MOH and NOH in deionized water to obtain a mixed solution, adding the mixed solution into a reaction kettle, heating to a certain temperature, carrying out hydrothermal reaction, washing the obtained reactant, carrying out solid-liquid separation and drying to obtain a hybrid phosphate open framework material M x N 2-x [(VO) 2 (HPO 4 ) 2 (C 2 O 4 )](ii) a The MOH is LiOH or KOH, and the NOH is KOH;
(2) Dispersing the obtained hybrid phosphate open framework material in a non-aqueous solvent, adding a surfactant, continuously stirring, and then carrying out solid-liquid separation and cleaning to obtain a modified hybrid phosphate open framework material; the surfactant is one or more of 3-aminopropyltriethoxysilane, hexadecyl trimethyl ammonium bromide and poly diallyl dimethyl ammonium chloride;
(3) Dispersing the modified hybrid phosphate open framework material uniformly in a non-aqueous solvent, adding a high-nickel anode material, continuously stirring to ensure that the modified hybrid phosphate open framework material is uniformly coated on the high-nickel anode material, and then carrying out solid-liquid separation, washing and drying to obtain a hybrid phosphate open framework composite high-nickel anode material; the mass ratio of the modified hybrid phosphate open frame material to the high-nickel anode material is 2-10%.
2. A preparation method of a hybrid phosphate open framework material composite high-nickel cathode material is characterized by comprising the following steps:
(1) Phosphoric acid, oxalic acid and V 2 O 5 Dissolving alkali metal hydroxide MOH and NOH in deionized water to obtain a mixed solution, adding the mixed solution into a reaction kettle, heating to a certain temperature, carrying out hydrothermal reaction, washing the obtained reactant with water, carrying out solid-liquid separation and drying to obtain a hybrid phosphate open framework material M x N 2-x [(VO) 2 (HPO 4 ) 2 (C 2 O 4 )](ii) a The MOH is LiOH or KOH, and the NOH is KOH;
(2) Dispersing the obtained hybrid phosphate open framework material in a non-aqueous solvent, adding a surfactant, continuously stirring, and then carrying out solid-liquid separation and cleaning to obtain a modified hybrid phosphate open framework material; the surfactant is one or more of 3-aminopropyltriethoxysilane, hexadecyl trimethyl ammonium bromide and poly diallyl dimethyl ammonium chloride;
(3) Dispersing the modified hybrid phosphate open framework material uniformly in a non-aqueous solvent, adding a high-nickel anode material, continuously stirring to ensure that the modified hybrid phosphate open framework material is uniformly coated on the high-nickel anode material, and then carrying out solid-liquid separation, washing and drying to obtain the hybrid phosphate open framework composite high-nickel anode material.
3. The preparation method of the hybrid phosphate open framework material composite nickelic material according to claim 2, wherein in the step (2), the dosage ratio of the hybrid phosphate open framework material, the surfactant and the non-aqueous solvent is 0.1-0.5 g.
4. The method for preparing the hybrid phosphate open framework material composite nickelic material according to claim 2, wherein in the step (1), the mixed solution contains oxalic acid and oxalic acid in molar ratio 2 O 5 The total amount of MOH and NOH is 1-10.
5. The preparation method of the hybrid phosphate open framework material composite high-nickel cathode material according to any one of claims 2 to 4, wherein in the step (1), the temperature rise speed is 1-2 ℃/min; the temperature of the hydrothermal reaction is 100-160 ℃; the time of the hydrothermal reaction is 20-30 h.
6. The method for preparing the hybrid phosphate open framework material composite high-nickel cathode material according to any one of claims 2 to 4, wherein the continuous stirring time in the step (2) is 10 to 18 hours.
7. The method for preparing the hybrid phosphate open framework material composite nickelic material according to any one of claims 2 to 4, characterized in that in the step (1), the drying temperature is 40 to 60 ℃;
in the step (1), before adding the obtained mixed solution into the reaction kettle, the ultrasonic treatment of the mixed solution is also included.
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