CN112186151A - Cobalt phosphide nanoparticle inlaid carbon nanosheet array material and preparation and application thereof - Google Patents

Cobalt phosphide nanoparticle inlaid carbon nanosheet array material and preparation and application thereof Download PDF

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CN112186151A
CN112186151A CN202010976075.9A CN202010976075A CN112186151A CN 112186151 A CN112186151 A CN 112186151A CN 202010976075 A CN202010976075 A CN 202010976075A CN 112186151 A CN112186151 A CN 112186151A
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cobalt phosphide
carbon
nanoparticle
nanosheet array
cobalt
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严微微
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China Jiliang University
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5805—Phosphides
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    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a cobalt phosphide nanoparticle inlaid carbon nanosheet array material, a preparation method thereof and application of the cobalt phosphide nanoparticle inlaid carbon nanosheet array material in a lithium ion battery cathode material. In the cobalt phosphide nanoparticle-embedded carbon nanosheet array material, cobalt phosphide nanoparticles are embedded in the carbon nanosheets to form a date cake type composite structure; the carbon nano-sheet vertically grows on the surface of the foam nickel to form an array structure. The preparation method comprises the following steps: firstly growing a ZIF-67 nanosheet array on the surface of foamed nickel, and then carbonizing and phosphorizing. The invention can improve the conductivity, structural stability and cycling stability of cobalt phosphide and electrochemical activity, so that the cobalt phosphide has higher charge and discharge capacity and more stable cycling performance. The cobalt phosphide nanoparticle mosaic carbon nanosheet array has important application value as a lithium ion battery cathode material.

Description

Cobalt phosphide nanoparticle inlaid carbon nanosheet array material and preparation and application thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a cobalt phosphide nanoparticle inlaid carbon nanosheet array material and preparation and application thereof.
Background
The lithium ion battery has the advantages of high energy density and power density, long cycle life, no memory effect and the like, and is widely used in portable electronic equipment and electric automobiles. At present, graphite is mainly used as a negative electrode material of a commercial lithium ion battery, but the theoretical capacity of the graphite is only 372mAh g-1The graphite has poor safety performance and low rate performance, so that the development of a negative electrode material with higher energy density and better cycle stability is the key point of the research of the lithium ion battery.
The metal phosphide has higher specific capacity than graphite, and is an ideal substitute material of graphite, such as cobalt phosphide (CoP)3) The theoretical capacity reaches 1620mAh g-1. But not cobalt phosphide (CoP)3) When the metal phosphide is used as the lithium ion battery cathode material, the problems of low conductivity, low lithium ion migration rate, large volume expansion, poor cycle stability and the like exist, and cobalt phosphide (CoP) is severely restricted3) And the like in lithium ion batteries.
In order to improve the lithium storage performance of cobalt phosphide, the current method is mainly a composite conductive material. Patent specification with publication number CN111525127A discloses a graphene-based cobalt phosphide cathode material and preparation and application thereof, which adopts Graphene Oxide (GO) with a two-dimensional structure as a substrate material, compounds the graphene with ZIF-67, reduces the composite material, and then obtains a graphene-coated cobalt phosphide composite material by calcining and phosphating the obtained aerogel, but the cobalt phosphide synthesized by the method has a large size and is coated in coarse carbon particles, and the lithium storage reaction of the cobalt phosphide is severely limited. Lihong Xue et al reported that CoP3@ PPy nanocube materials (Qing Liu, Yu Luo, Weilun Chen, Youwei Yan, Lihong Xue, Wuxing Zhang, Chemical Engineering Journal 347(2018)455-461), they will use the precursor cubic Co3[Co(CN)6]2After phosphorization into cobalt phosphide, a layer of PPy is coated, and the material also has CoP3Problem of oversizing, CoP3The size of the cube reachesAbout 2 μm, which is obviously unfavorable for the lithium storage reaction and has poor stability. At present, the research progress of cobalt phosphide in the field of lithium ion batteries is slow, and a new breakthrough is needed in the aspects of nano structure design, composite high-conductivity materials and the like.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a cobalt phosphide nanoparticle inlaid carbon nanosheet array material.
A cobalt phosphide nanoparticle mosaic carbon nanosheet array material, cobalt phosphide (CoP)3) The nano particles are embedded in the carbon nano sheets to form a jujube cake type composite structure; the carbon nano-sheet vertically grows on the surface of the foam nickel to form an array structure.
The particle size of the cobalt phosphide nano-particles is 5-60 nm.
The thickness of the carbon nano sheet is 50-300nm, and the growth height of the carbon nano sheet on the foamed nickel is 1-5 mu m.
The carbon nanosheet is amorphous carbon and is formed by carbonizing a ZIF-67 nanosheet.
The invention also provides a preferable preparation method of the cobalt phosphide nanoparticle mosaic carbon nanosheet array material, which comprises the following steps:
(1) mixing Co (NO)3)2·6H2Mixing the O aqueous solution and the 2-methylimidazole aqueous solution, adding foamed nickel, controlling the temperature of the mixed solution to be 0-50 ℃, standing for 30-300min, taking out the foamed nickel, washing and drying to obtain a ZIF-67 nanosheet array @ foamed nickel;
(2) the ZIF-67 nanosheet array @ foamed nickel obtained in the step (1) is subjected to argon protection at the temperature of 1-5 ℃ for min-1Heating to 500-600 ℃, preserving the heat for 30-120min, and cooling to room temperature to obtain a cobalt nanoparticle inlaid carbon nanosheet array @ foamed nickel;
(3) embedding the cobalt nanoparticle inlaid carbon nanosheet array @ foam nickel obtained in the step (2) in NaH2PO2Adding into the powder under the protection of argon gas at 5-10 deg.C for min-1Heating to 350-450 ℃, preserving the heat for 30-120min, and cooling to room temperature to obtain the cobalt phosphide nanoparticle inlaid carbon nanosheet array @ foamed nickel.
According to the invention, a ZIF-67 nanosheet array grows on the surface of foamed nickel, and then carbonization and phosphorization are carried out.
In a preferred embodiment, in step (1), the Co (NO) is3)2·6H2O aqueous solution made of 0.73g Co (NO)3)2·6H2O is dissolved in 50mL of deionized water, and the 2-methylimidazole aqueous solution is prepared by dissolving 1.64g of 2-methylimidazole in 50mL of deionized water.
Preferably, the foamed nickel is cleaned by hydrochloric acid and deionized water before use and is dried in vacuum. The hydrochloric acid is preferably dilute hydrochloric acid with HCl mass fraction not more than 20%.
Preferably, in step (1), the temperature for drying is 80 ℃.
The invention also provides application of the cobalt phosphide nanoparticle mosaic carbon nanosheet array material in a lithium ion battery cathode material.
In a preferable example, the cobalt phosphide nanoparticle-embedded carbon nanosheet array @ foam nickel is directly used as a working electrode, and is assembled with a lithium sheet and a diaphragm into a CR2025 button-type lithium ion battery in a glove box filled with high-purity argon. The electrolyte is 1mol L-1LiPF6The EC/DMC electrolyte adopts a new power battery test system to test the charge-discharge performance and the cycle performance of the lithium ion battery.
The invention can improve the conductivity, structural stability and cycling stability of cobalt phosphide and electrochemical activity, so that the cobalt phosphide has higher charge and discharge capacity and more stable cycling performance.
Compared with the prior art, the invention has the main advantages that:
(1) the cobalt phosphide nano-particles have small size, so that the lithium ion migration rate is improved, and the electrochemical activity of the lithium storage reaction of the cobalt phosphide is improved; and the small size brings the absolute value reduction of the volume expansion of the cobalt phosphide, and is beneficial to improving the integral structural stability of the composite material, thereby obviously improving the cycle performance of the cobalt phosphide.
(2) The cobalt phosphide nano-particles are dispersed in the carbon sheet, and the composite structure not only obviously improves the conductivity of the cobalt phosphide, but also effectively limits the volume expansion of the cobalt phosphide, and further improves the structural stability and the charge-discharge cycle performance of the cobalt phosphide.
(3) The carbon sheet is very thin, so that the lithium ion diffusion path is shortened, and the lithium ions can rapidly reach the cobalt phosphide; the carbon sheets are erected on the surface of the foamed nickel, two sides of each carbon sheet can be contacted with electrolyte, and lithium ions can be transmitted inwards from two sides of the carbon sheets, so that the lithium ion diffusion path is further shortened, and the electrode reaction kinetics are improved; the carbon sheet is connected with the foamed nickel, and traditional chemical glue such as PVDF (polyvinylidene fluoride) is not used, so that the good conductivity of each carbon sheet is ensured, and the charge and discharge performance, particularly the rate performance, of the cobalt phosphide is remarkably improved.
Drawings
FIG. 1 is an SEM photograph of a ZIF-67 nanosheet array @ nickel foam prepared in example 1, scale: 10 mu m;
fig. 2 is an SEM photograph of cobalt nanoparticle-intercalated carbon nanosheet array @ nickel foam prepared in example 1, scale: 200 nm;
fig. 3 is an SEM photograph of cobalt phosphide nanoparticle-inlaid carbon nanosheet array @ nickel foam prepared in example 1, scale: 2 μm;
FIG. 4 is a TEM photograph of an array of cobalt phosphide nanoparticle-inlaid carbon nanosheets prepared in example 1;
FIG. 5 shows the current density of 200mA g of the cobalt phosphide nanoparticle-embedded carbon nanosheet array material prepared in example 1-1A cycle performance map of (a);
fig. 6 is a rate performance graph of the cobalt phosphide nanoparticle-inlaid carbon nanosheet array material prepared in example 1.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
(1) Cleaning the foamed nickel with dilute hydrochloric acid and deionized water, and drying in vacuum. 0.73g Co (NO)3)2·6H2Dissolving O in 50mL of deionized water, dissolving 1.64g of 2-methylimidazole in 50mL of deionized water, quickly mixing the two solutions, suspending the nickel foam in the mixed solution, standing for 60min at the temperature of 35 ℃, taking out, washing with deionized water for several times, and drying in an oven at the temperature of 80 ℃ to obtain ZIF-67 nanosheet array @ nickel foam;
(2) putting the ZIF-67 nanosheet array @ foamed nickel obtained in the step (1) into a quartz tube furnace, and heating at the speed of 1 ℃ for min under the protection of argon-1Heating to 550 ℃, preserving heat for 60min, and cooling to room temperature along with the furnace to obtain cobalt nanoparticle embedded carbon nanosheet array @ foamed nickel;
(3) embedding the cobalt nanoparticle inlaid carbon nanosheet array @ foam nickel obtained in the step (2) in NaH2PO2Putting the powder into a quartz tube furnace, and heating at the temperature of 10 ℃ for min under the protection of argon-1Heating to 400 ℃, preserving heat for 60min, and cooling to room temperature along with the furnace to obtain the cobalt phosphide nanoparticle inlaid carbon nanosheet array @ foamed nickel.
FIG. 1 is an SEM photograph of the ZIF-67 nanosheet array @ nickel foam synthesized in step (1). ZIF-67 nanometer sheets uniformly grow on the surface of the foamed nickel in an upright mode, a typical array structure is presented, obvious gaps exist among the nanometer sheets, the thickness of the nanometer sheets is about 150nm, and the height of the nanometer sheets is about 2 microns. Fig. 2 is an SEM photograph of cobalt nanoparticle mosaic carbon nanosheet array @ nickel foam after carbonization in step (2). Due to carbonization, the nano-sheet shrinks and the thickness becomes 100nm, but the array structure is not destroyed, the nano-sheet still stands perfectly on the surface of the foam nickel, and a plurality of inlaid cobalt nano-particles are displayed on the surface of the nano-sheet. FIG. 3, step (3), is an SEM photograph of a phosphated cobalt phosphide nanoparticle-inlaid carbon nanosheet array @ nickel foam, with the array structure still intact. The surface of the nanosheet becomes smooth as a result of the phosphating reaction. Fig. 4 is a TEM photograph of the cobalt phosphide nanoparticle-inlaid carbon nanosheet array material, and it can be seen that the cobalt phosphide nanoparticles, having a particle size of about 5-10nm, are uniformly inlaid on the amorphous carbon substrate.
The cobalt phosphide nanoparticle mosaic carbon nanosheet array material is used as a working electrode of a lithium ion battery, and a hand filled with high-purity argon gas is usedThe interior of the sleeve box, a metal lithium sheet and a diaphragm form a CR2025 button type lithium ion battery. The electrolyte is 1mol L-1LiPF6The EC/DMC electrolyte adopts a novacan battery test system to test the charge-discharge performance and the cycle stability of the lithium ion battery, and the charge-discharge current density is 200mAg-1The voltage range is 0.01-3.0V.
FIG. 5 shows the current density of the cobalt phosphide nanoparticle-inlaid carbon nanosheet array material at 200mAg-1Cycle performance map of (c). The 1 st cycle discharge capacity was 1419mAh g-1And the discharge capacity is reduced to 919mAh g by 13 th cycle-1And then the discharge capacity is relatively stable, and the discharge capacity is 787mAh g by the 200 th cycle-1. Average discharge capacity of 200 cycles 842mAh g-1. The discharge capacity and cycling stability of cobalt phosphide nanoparticle mosaic carbon nanosheet arrays exceeded that of the patent technology published under No. CN111525127A and the work of Lihong Xue et al (Qing Liu, Yu Luo, Weilun Chen, Youwei Yan, Lihong Xue, Wuxing Zhang, Chemical Engineering Journal 347(2018) 455-) 461).
Fig. 6 is a rate performance graph of cobalt phosphide nanoparticle mosaic carbon nanosheet array material. At 100mAg-1Under the current density, the discharge capacity of the cobalt phosphide nanoparticle mosaic carbon nanosheet array is 1460mAh g from the first circulation-1Reduce to 1122mAh g in the 10 th cycle-1And the lithium ion battery has particularly high specific discharge capacity and high electrochemical activity. When the current density increased to 500mA g-1，1000mA g-1And 2000mA g-1The average discharge capacity was 1001mAh g in this order-1，854mAh g-1663mAh g-1And excellent rate capability is presented. When the current is reduced to 500mA g again-1The discharge capacity is recovered to 919mAh g-1And the recovery rate reaches 91.8 percent, which means that the cobalt phosphide nanoparticle mosaic carbon nanosheet array has quite high structural stability, circulation stability and reversibility and can bear charge-discharge reaction of larger current.
The cobalt phosphide nanoparticle mosaic carbon nanosheet array has excellent electrochemical lithium storage performance, including high discharge capacity, stable cycle performance and excellent rate capability, which is a result of the nano-size of cobalt phosphide, a date cake type mosaic composite structure in amorphous carbon and the comprehensive effect of the carbon nanosheet array structure.
Example 2
Cleaning the foamed nickel with dilute hydrochloric acid and deionized water, and drying in vacuum. 0.73g of Co (NO)3)2·6H2Dissolving O in 50mL of deionized water, dissolving 1.64g of 2-methylimidazole in 50mL of deionized water, quickly mixing the two solutions, suspending the nickel foam in the mixed solution, standing for 120min at the temperature of 35 ℃, taking out, washing with deionized water for several times, and drying in an oven at 80 ℃ to obtain ZIF-67 nanosheet array @ nickel foam; the subsequent process was the same as in example 1.
The microstructure of the product cobalt phosphide nanoparticle mosaic carbon nanosheet array was similar to that of example 1, with the primary difference being that the thickness of the carbon nanosheet became 150 nm.
The same process as in example 1 was used to fabricate a negative electrode of a lithium ion battery, which was assembled into a lithium ion battery at a current density of 200mA g-1And carrying out cyclic charge and discharge test within the voltage range of 0.01-3.0V. The discharge capacity at cycle 1 was 1301mAh g-1And the discharge capacity is reduced to 861mAh g by the 19 th cycle-1The discharge capacity was then relatively smooth and was 716mAh g by the 200 th cycle-1. Average discharge capacity 772mAh g of 200 cycles-1。
Example 3
Cleaning the foamed nickel with dilute hydrochloric acid and deionized water, and drying in vacuum. 0.73g Co (NO)3)2·6H2Dissolving O in 50mL of deionized water, dissolving 1.64g of 2-methylimidazole in 50mL of deionized water, quickly mixing the two solutions, suspending the nickel foam in the mixed solution, standing for 60min at the temperature of 25 ℃, taking out, washing with deionized water for several times, and drying in an oven at 80 ℃ to obtain ZIF-67 nanosheet array @ nickel foam; the subsequent process was the same as in example 1.
The microstructure of the product cobalt phosphide nanoparticle mosaic carbon nanosheet array was similar to that of example 1, with the primary difference being that the thickness of the carbon nanosheet became 90 nm.
The same process as in example 1 was used to fabricate a negative electrode of a lithium ion battery, which was assembled into a lithium ion battery at a current density of 200mA g-1And carrying out cyclic charge and discharge test within the voltage range of 0.01-3.0V. The 1 st cycle discharge capacity was 1468mAh g-1The discharge capacity dropped to 959mAh g by 12 th cycle-1After that, the discharge capacity was relatively smooth, and the discharge capacity was 811mAh g to the 200 th cycle-1. Average discharge capacity 880mAh g for 200 cycles-1。
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.

Claims (7)

1. A cobalt phosphide nanoparticle-embedded carbon nanosheet array material is characterized in that cobalt phosphide nanoparticles are embedded in carbon nanosheets to form a date cake type composite structure; the carbon nano-sheet vertically grows on the surface of the foam nickel to form an array structure.
2. The cobalt phosphide nanoparticle-inlaid carbon nanosheet array material of claim 1, wherein the cobalt phosphide nanoparticles have a particle size of 5-60 nm;
the thickness of the carbon nano sheet is 50-300nm, and the growth height of the carbon nano sheet on the foamed nickel is 1-5 mu m;
the carbon nanosheet is amorphous carbon and is formed by carbonizing a ZIF-67 nanosheet.
3. The preparation method of the cobalt phosphide nanoparticle-inlaid carbon nanosheet array material as claimed in claim 1 or claim 2, comprising the steps of:
(1) mixing Co (NO)3)2·6H2Mixing the O aqueous solution and the 2-methylimidazole aqueous solution, adding foamed nickel, controlling the temperature of the mixed solution to be 0-50 ℃, standing for 30-300min, taking out the foamed nickel, washing and drying to obtain a ZIF-67 nanosheet array @ foamed nickel;
(2) preparing ZIF-67 nanosheets obtained in the step (1)Array @ foamed nickel is put under the protection of argon at 1-5 ℃ for min-1Heating to 500-600 ℃, preserving the heat for 30-120min, and cooling to room temperature to obtain a cobalt nanoparticle inlaid carbon nanosheet array @ foamed nickel;
(3) embedding the cobalt nanoparticle inlaid carbon nanosheet array @ foam nickel obtained in the step (2) in NaH2PO2Adding into the powder under the protection of argon gas at 5-10 deg.C for min-1Heating to 350-450 ℃, preserving the heat for 30-120min, and cooling to room temperature to obtain the cobalt phosphide nanoparticle inlaid carbon nanosheet array @ foamed nickel.
4. The method according to claim 3, wherein in the step (1), the Co (NO) is used3)2·6H2O aqueous solution made of 0.73g Co (NO)3)2·6H2O is dissolved in 50mL of deionized water, and the 2-methylimidazole aqueous solution is prepared by dissolving 1.64g of 2-methylimidazole in 50mL of deionized water.
5. The preparation method of claim 3, wherein the foamed nickel is cleaned by hydrochloric acid and deionized water before use, and is dried in vacuum.
6. The production method according to claim 3, wherein the temperature of the drying in the step (1) is 80 ℃.
7. The application of the cobalt phosphide nanoparticle-inlaid carbon nanosheet array material of claim 1 or 2 in a lithium ion battery cathode material.
CN202010976075.9A 2020-09-16 2020-09-16 Cobalt phosphide nanoparticle inlaid carbon nanosheet array material and preparation and application thereof Pending CN112186151A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112992554A (en) * 2021-02-07 2021-06-18 广州大学 Foamed nickel-cobalt diselenide composite material and preparation method and application thereof
CN114725353A (en) * 2022-04-29 2022-07-08 长江师范学院 Novel metal chalcogenide solid solution electrode material and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109603883A (en) * 2018-12-29 2019-04-12 南京大学 A kind of@nanometers of phosphatization cobalt composite catalysts of N doping porous carbon polyhedron and preparation method thereof that can efficiently activate persulfate
CN110721724A (en) * 2019-10-30 2020-01-24 黑龙江科技大学 Nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles and preparation method and application thereof
CN110767466A (en) * 2019-10-08 2020-02-07 电子科技大学 Ni-doped CoP (cobalt phosphide) electrode material of super capacitor3Preparation method of foamed nickel
CN110931795A (en) * 2019-12-04 2020-03-27 南京工业大学 Flexible self-supporting composite electrode and preparation method and application thereof
CN111525127A (en) * 2020-04-09 2020-08-11 上海应用技术大学 Graphene-based cobalt phosphide cathode material and preparation and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109603883A (en) * 2018-12-29 2019-04-12 南京大学 A kind of@nanometers of phosphatization cobalt composite catalysts of N doping porous carbon polyhedron and preparation method thereof that can efficiently activate persulfate
CN110767466A (en) * 2019-10-08 2020-02-07 电子科技大学 Ni-doped CoP (cobalt phosphide) electrode material of super capacitor3Preparation method of foamed nickel
CN110721724A (en) * 2019-10-30 2020-01-24 黑龙江科技大学 Nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles and preparation method and application thereof
CN110931795A (en) * 2019-12-04 2020-03-27 南京工业大学 Flexible self-supporting composite electrode and preparation method and application thereof
CN111525127A (en) * 2020-04-09 2020-08-11 上海应用技术大学 Graphene-based cobalt phosphide cathode material and preparation and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112992554A (en) * 2021-02-07 2021-06-18 广州大学 Foamed nickel-cobalt diselenide composite material and preparation method and application thereof
CN114725353A (en) * 2022-04-29 2022-07-08 长江师范学院 Novel metal chalcogenide solid solution electrode material and preparation method and application thereof

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