CN109768260B - Cobaltoside/carbon composite material and preparation method and application thereof - Google Patents
Cobaltoside/carbon composite material and preparation method and application thereof Download PDFInfo
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- CN109768260B CN109768260B CN201910063119.6A CN201910063119A CN109768260B CN 109768260 B CN109768260 B CN 109768260B CN 201910063119 A CN201910063119 A CN 201910063119A CN 109768260 B CN109768260 B CN 109768260B
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Abstract
The invention provides a cobalt phosphide/carbon composite material and a preparation method and application thereof. The cobaltous phosphide/carbon composite material provided by the invention comprises a carbon material substrate and Co embedded in the carbon material substrate2P nano-sheet. The preparation method comprises the following steps: (1) mixing a cobalt source, a phosphorus source, a surfactant and water, and carrying out hydrothermal reaction to obtain Co2P precursor; (2) mixing Co2Mixing the P precursor with an organic carbon source solution, and carrying out hydrothermal reaction to obtain Co2A P/C composite material precursor; (3) mixing Co2And calcining the precursor of the P/C composite material in a protective atmosphere to obtain the cobaltous phosphide/carbon composite material. The cobaltous phosphide/carbon composite material provided by the invention has the advantages of good conductivity, high specific capacity, good rate capability and good cycle performance. The preparation method provided by the invention has the advantages of cheap and easily available raw materials, simple preparation process and strong operation controllability.
Description
Technical Field
The invention belongs to the field of new energy materials, relates to an electrode material, and particularly relates to a cobaltous phosphide/carbon composite material as well as a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, light weight, small volume, good cycle performance, environmental friendliness, no memory effect and the like, and is widely applied to various fields of electronic products, electric automobiles, large-scale energy storage and the like. However, the problems of shortage and uneven distribution of lithium resources in the earth crust are not enough to meet the increasing demand of people on the lithium ion battery, which seriously restricts the large-scale application of the lithium ion battery. Therefore, development of a novel secondary battery with abundant resources, low cost and excellent performance has become a new development trend and a research hotspot in the field of battery materials.
In recent years, sodium and potassium ion batteries have attracted extensive attention by researchers, and are considered to be ideal candidates for replacing lithium ion batteries as next-generation energy storage power sources because sodium, potassium and lithium belong to the same main group elements and have similar physicochemical properties. Meanwhile, the sodium and potassium elements are widely distributed, the resources are rich, the price is low, and the like, so that the method is more in line with the requirements of large-scale energy storage application. Therefore, sodium/potassium ion batteries have also received much attention from many researchers as new energy storage devices.
However, since the radius of both sodium and potassium ions is larger than that of lithium ions, the requirements for an electrode material capable of freely extracting sodium and potassium ions are more severe. When the traditional graphite cathode is used as the cathode of the sodium-ion battery, the specific capacity is lower when sodium ions are inserted and removed, and the development of the sodium-ion battery is severely restricted. Although the traditional graphite negative electrode can reversibly remove and insert potassium ions, the theoretical specific capacity of the graphite negative electrode as a negative electrode of a potassium ion battery is only 279 mAh/g. Therefore, research and development of a new sodium and potassium ion battery anode material are very important.
Co2P, as a metal gap compound, has the advantages of high theoretical specific capacity, high chemical stability, high conductivity, low cost, less polarization in the charge-discharge process, and the like, and has been widely used as a negative electrode material of a lithium ion battery. However, pure Co2The repeated de-intercalation process of the P material easily leads the volume change of the electrode to be gradually pulverized and failed, and leads the electrochemical performance of the battery to be poor.
CN102347474A discloses a high-capacity lithium ion battery cathode and a preparation method thereof, comprising an electrode substrate and a cathode film on the surface of the substrate, wherein the cathode film on the surface of the substrate is a cobalt phosphide film; mixing metal cobalt powder and red phosphorus powder according to the molar ratio of 1: 1-3, uniformly mixing, grinding, and tabletting to obtain a target for pulse laser deposition; b. placing a target and a substrate into a vacuum deposition chamber, wherein the distance between the target and the substrate is 25-50mm, the working gas is argon atmosphere, and the temperature of the substrate is 500-; c. the laser beam of the laser is focused by the lens and then is incident on the rotating target, and the particles excited by the laser beam are sputtered on the substrate. The method has complicated steps and expensive used instruments, and the prepared cobalt phosphide film has the problem that the electrochemical performance needs to be improved, so the method is not suitable for sodium/potassium ion batteries.
CN107403911A discloses a graphene/transition metal phosphide/carbon-based composite material, a preparation method thereof and a negative electrode of a lithium ion battery. The compound formed by transition metal iron, cobalt or nickel and phosphorus in the graphene/transition metal phosphide/carbon composite material. In the composite material, graphene is used as a matrix, and transition metal phosphide nano particles with a good nano structure are used as a load to construct a graphene/transition metal phosphide composite material; and simultaneously, the amorphous carbon is utilized to carry out modification such as coating, filling, connection and the like on the composite material, so as to obtain the graphene/transition metal phosphide/carbon ternary nanocomposite material. Although the electrochemical performance of the scheme is satisfactory, the composite material needs to use graphene, the raw material cost is high, and the preparation process is complicated.
CN106111171A discloses a preparation method of cobalt phosphide wrapped by a carbon layer, which adopts cobalt salt and an organic ligand as raw materials, firstly synthesizes a metal organic framework material containing cobalt, and then synthesizes cobalt phosphide wrapped by the carbon layer through high-temperature pyrolysis, air oxidation and low-temperature phosphating in sequence. Although the preparation cost is relatively low, the product cannot be used for a battery pole piece and can only be used as a catalyst.
Therefore, a Co which has simple preparation method, high conductivity, good cycle and rate performance and is suitable for a sodium/potassium ion battery is developed2P/C composites are of great interest to the art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a cobaltous phosphide/carbon composite material and a preparation method and application thereof. The invention provides cobaltous phosphide/carbon (Co)2The P/C) composite material has the advantages of high conductivity, high specific capacity, good cycle and rate performance, cheap and easily-obtained raw materials, simple preparation process and strong operation controllability.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a cobaltous phosphide/carbon composite material comprising a carbon material substrate and Co embedded in the carbon material substrate2P nano-sheet.
Co provided by the invention2Co of P/C composite material2The P nanosheets are embedded into the carbon material substrate, so that the problem of volume change of phosphide particles in the ion intercalation and deintercalation process is solved, and the cycle stability of the composite material is improved. On the other hand, the synergistic effect between carbon and phosphide improves the specific capacity and rate capability of the composite material.
In the cobalt phosphide/carbon composite material provided by the invention, Co2The P nano sheets are uniformly distributed in the carbon material substrate, which is helpful for improving the electrical conductivity of the composite material.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
As a preferred embodiment of the present invention, the Co is2The P nanosheet is monodisperse Co2P nano-sheet.
Preferably, the Co2The size of the P nanosheets is 1-6 μm, for example 1 μm, 2 μm, 3 μm, 4 μm, 5 μm or 6 μm, but is not limited to the recited values, and other values not recited within this range of values are equally applicable. In the present invention, if Co is present2The overlarge size of the P nanosheet can cause slow ion diffusion; if Co is present2The undersize of the P nanosheets can cause the flaky particles to be crushed, and the transmission of ions is influenced. Here, what isSaid dimensions are Co2The length of the longest side of the P nano sheet.
Preferably, the Co2The thickness of the P nanosheet is 3 to 14nm, for example 3nm, 5nm, 7nm, 9nm, 10nm, 11nm, 12nm or 14nm, but is not limited to the recited values and other values not recited within the range of values are equally applicable. In the present invention, if Co is present2The thickness of the P nano sheet is too large, so that an ion transmission path is enlarged, and ion diffusion is slowed; if Co is present2The thickness of the P nano-sheet is too small, which easily causes particle pulverization and structure collapse.
Preferably, the cobaltous phosphide/carbon composite material has a layered structure. The layered structure can increase the specific surface area of the composite material and is beneficial to enriching the pore structure.
Preferably, in the cobalt phosphide/carbon composite material, a carbon material substrate and Co2The mass ratio of the P nanosheets is 0.1:1 to 0.5:1, for example 0.1:1, 0.2:1, 0.3:1, 0.4:1 or 0.5:1, but is not limited to the recited values, and other values not recited within this range of values are equally applicable. In the present invention, if the carbon material substrate is Co2The mass ratio of the P nanosheets is too large (i.e., Co)2Too few P nanosheets), which can result in too thick a coated carbon layer and hinder the transmission of ions; if the carbon material substrate is Co2The mass ratio of the P nanosheets is too small (i.e., Co)2Too many P nanosheets), which can result in too thin a coated carbon layer, small increase in conductivity, and also affect ion transport and thus electrochemical performance
Preferably, the specific surface area of the cobalt phosphide/carbon composite material is 220-260m2g-1E.g. 220m2g-1、230m2g-1、240m2g-1、250m2g-1Or 260m2g-1And the like, but are not limited to the recited values, and other values not recited within the numerical range are also applicable.
Preferably, the cobalt phosphide/carbon composite material is a porous material.
In the invention, the cobalt phosphide/carbon composite material is a porous material, has rich pore structure, is beneficial to the rapid migration of ions and electrons, can effectively relieve the volume change of the active material in the ion intercalation and deintercalation process in the circulation process, enables the structure to be stable, and improves the electrochemical performance of the material.
Preferably, the porosity of the cobalt phosphide/carbon composite is 30% to 60%, such as 30%, 35%, 40%, 50%, 55%, or 60%, and the like, but is not limited to the recited values, and other values not recited within this range are equally applicable.
Preferably, the pore size of the cobalt phosphide/carbon composite is 1-10nm, such as 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm or 10nm, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
In a second aspect, the present invention provides a process for preparing a cobalt phosphide/carbon composite material as defined in the first aspect, said process comprising the steps of:
(1) mixing a cobalt source, a phosphorus source, a surfactant and water, and carrying out hydrothermal reaction to obtain Co2P precursor;
(2) mixing the Co of step (1)2Mixing the P precursor with an organic carbon source solution, and carrying out hydrothermal reaction to obtain Co2A P/C composite material precursor;
(3) mixing the Co of the step (2)2And calcining the precursor of the P/C composite material in a protective atmosphere to obtain the cobaltous phosphide/carbon composite material.
The preparation method provided by the invention adopts a two-step hydrothermal method to prepare Co2The P/C composite material has the advantages of cheap and easily-obtained raw materials, simple preparation process and strong operation controllability. The first step of hydrothermal reaction aims at synthesizing pure-phase Co2P precursor, the second step of hydrothermal reaction aims at coating organic carbon source on Co uniformly2P particle surface.
As a preferable technical scheme of the invention, the cobalt source in the step (1) is soluble cobalt salt.
Preferably, the soluble cobalt salt comprises any one of cobalt nitrate, cobalt acetate or cobalt chloride or a combination of at least two thereof. Here, the cobalt nitrate, acetate or chloride includes not only pure substances but also their corresponding hydrates, such as cobalt nitrate hexahydrate, cobalt acetate tetrahydrate or cobalt chloride hexahydrate, and the like.
Preferably, the phosphorus source of step (1) comprises red phosphorus.
Preferably, the molar ratio of the cobalt source to the phosphorus source in step (1) is 1:4.5 to 1:6.0, such as 1:4.5, 1:5, 1:5.5 or 1:6, but not limited to the recited values, and other values not recited in this range are equally applicable.
Preferably, the surfactant in step (1) comprises any one of cetyltrimethylammonium bromide (CTAB), polyvinylpyrrolidone (PVP) or Sodium Dodecylbenzenesulfonate (SDBS), or a combination of at least two thereof. Typical but non-limiting combinations are a combination of CTAB and PVP, a combination of CTAB and SDBS, a combination of PVP and SDBS, and the like.
Preferably, the concentration of the surfactant in the hydrothermal reaction system of step (1) is 1.43-4.29g/L, such as 1.43g/L, 1.5g/L, 2.0g/L, 2.5g/L, 3.0g/L, 3.5g/L, 4.0g/L, or 4.29g/L, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable. The hydrothermal reaction system is a hydrothermal reaction system composed of a cobalt source, a phosphorus source, a surfactant, and water.
Preferably, the mixing method in the step (1) is stirring mixing.
As a preferred embodiment of the present invention, the temperature of the hydrothermal reaction in step (1) is 140-220 ℃, for example, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃ or 220 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the hydrothermal reaction time in step (1) is 15-60h, such as 15h, 20h, 25h, 30h, 35h, 40h, 45h, 50h, 55h or 60h, but not limited to the recited values, and other unrecited values in the range of the recited values are also applicable.
Preferably, the hydrothermal reaction of step (1) is carried out in a teflon-lined stainless steel autoclave.
Preferably, step (1) further comprises: to the Co2And washing and drying the P precursor.
Preferably, the washing method is washing with hydrochloric acid, and then washing with water and ethanol. For example, two washes with hydrochloric acid followed by several washes with deionized water and alcohol.
Preferably, the hydrochloric acid has a concentration of 1 to 3mol/L, such as 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, or 3mol/L, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
In a preferred embodiment of the present invention, in the step (2), the organic carbon source includes any one or a combination of at least two of glucose, sucrose, and citric acid. Typical but non-limiting combinations are: a combination of glucose and sucrose, a combination of glucose and citric acid, a combination of sucrose and citric acid, and the like.
Preferably, the concentration of the organic carbon source in the organic carbon source solution in step (2) is 0.05-0.5mol/L, such as 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L or 0.5mol/L, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, in step (2), the Co2The mass ratio of the P precursor to the organic carbon source is 1:0.15 to 1:0.55, for example, 1:0.15, 1:0.25, 1:0.35, 1:0.45 or 1:0.55, but the ratio is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable. Here, the Co2The mass of the P precursor is Co2The mass of the P precursor dry powder, i.e. the mass after drying.
As the preferred technical scheme of the method, the temperature of the hydrothermal reaction in the step (2) is 160-200 ℃, for example 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃, but the method is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the hydrothermal reaction time in step (2) is 2-5h, such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the hydrothermal reaction of step (2) is carried out in a teflon-lined stainless steel autoclave.
As a preferred technical scheme of the invention, the protective atmosphere in the step (3) comprises argon.
Preferably, the temperature of the calcination in step (3) is 500-700 deg.C, such as 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C or 700 deg.C, but not limited to the recited values, and other unrecited values within the range of values are equally applicable.
Preferably, the calcination time in step (3) is 2-6h, such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the temperature increase rate of the calcination in step (3) is 1-10 deg.C/min, such as 1 deg.C/min, 2 deg.C/min, 3 deg.C/min, 4 deg.C/min, 5 deg.C/min, 6 deg.C/min, 7 deg.C/min, 8 deg.C/min, 9 deg.C/min, or 10 deg.C/min, but is not limited to the values listed, and other values not listed in this range are equally applicable.
As a further preferable technical scheme of the preparation method, the method comprises the following steps:
(1) mixing soluble cobalt salt, red phosphorus, a surfactant and water, carrying out hydrothermal reaction in a stainless steel autoclave with a Teflon lining at the temperature of 140-2P precursor;
wherein the molar ratio of the soluble cobalt salt to the red phosphorus is 1:4.5-1: 6.0; in the hydrothermal reaction system, the concentration of the surfactant is 1.43-4.29 g/L;
(2) mixing the Co of step (1)2Mixing the P precursor with 0.05-0.5mol/L organic carbon source solution, and then carrying out hydrothermal reaction in a stainless steel high-pressure kettle with a Teflon lining, wherein the temperature of the hydrothermal reaction is 160-200 ℃, and the time of the hydrothermal reaction is 2-5h, so as to obtain Co2A P/C composite material precursor;
wherein said Co2The mass ratio of the P precursor to the organic carbon source is 1:0.15-1: 0.55;
(3) mixing the Co of the step (2)2And heating the precursor of the P/C composite material to 500-700 ℃ at the heating rate of 1-10 ℃/min in the argon atmosphere for calcining for 2-6h to obtain the cobaltous phosphide/carbon composite material.
In a third aspect, the present invention provides the use of a cobaltous phosphide/carbon composite material as described in the first aspect as an anode material for a sodium-ion battery or a potassium-ion battery.
The cobaltous phosphide/carbon composite material provided by the invention shows excellent cycle and rate performance when being applied to a sodium/potassium ion battery, and has a wide application prospect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the cobaltous phosphide/carbon composite material provided by the invention has the advantages of good conductivity, high specific capacity, good rate capability and cycle performance, and is particularly suitable for being used as a negative electrode material for sodium ion batteries or potassium ion batteries. The cobaltous phosphide/carbon composite material provided by the invention is used for sodium ion batteries, the first charge specific capacity of 50mA/g can reach 366.7mAh/g, the discharge specific capacity of 500mA/g can reach 301.2mAh/g, and the conductivity can reach 6.8 multiplied by 10-4The capacity retention rate of S/m and 50mA/g after 50 charge-discharge cycles can reach 80.1%; the cobaltous phosphide/carbon composite material provided by the invention is used for potassium ion batteries, the first charge specific capacity of 50mA/g can reach 297.2mAh/g, the discharge specific capacity of 500mA/g can reach 285.3mAh/g, and the conductivity can reach 5.2 multiplied by 10-4The capacity retention rate of S/m and 50mA/g after 50 charge-discharge cycles can reach 70.2%;
(2) the preparation method provided by the invention adopts a two-step hydrothermal method to prepare Co2The P/C composite material has the advantages of cheap and easily obtained raw materials, simple preparation process and strong operation controllability, and is suitable for industrial large-scale production.
Drawings
FIG. 1 shows Co prepared in example 1 of the present invention2P/C recombinationXRD pattern of the material;
FIG. 2 shows Co prepared in example 1 of the present invention2SEM image of P/C composite material;
FIG. 3 shows Co prepared in example 1 of the present invention2The P/C composite material is used as a sodium ion battery cathode material, and is used as a cycle performance test chart under the conditions that the voltage interval is 0.01-3.0V and the current density is 50 mA/g;
FIG. 4 shows Co prepared in example 2 of the present invention2And (3) taking the P/C composite material as a potassium ion battery cathode material, and testing the cycle performance of the P/C composite material under the conditions that the voltage interval is 0.01-3.0V and the current density is 50 mA/g.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
This example prepares Co as follows2P/C composite material:
(1) 0.6112g of Co (NO)3)2·6H2O, 0.3577g of red phosphorus and 0.05g of CTAB surfactant were added to 35mL of deionized water and magnetically stirred. Transferring the obtained suspension into a stainless steel autoclave with a 50mL Teflon lining, placing the stainless steel autoclave in an oven at 210 ℃, and reacting for 48 hours to obtain Co2And (3) P precursor. Then washing with 3mol/L hydrochloric acid twice, washing with deionized water and alcohol several times, and drying in a drying oven.
Wherein, Co (NO)3)2·6H2The molar ratio of O to red phosphorus was about 1:5.5, and the concentration of a surfactant (CTAB) in the suspension system used for the hydrothermal reaction was 1.43 g/L.
(2) Then 1g of dried Co was taken2Adding the P precursor into a 0.048mol/L glucose solution, transferring the solution into a 50mL stainless steel autoclave with a Teflon lining, placing the autoclave in an oven at 180 ℃, and reacting the solution 3h, obtaining Co2P/C composite material precursor.
Wherein said Co2The mass ratio of the P precursor to the organic carbon source (glucose) was 1: 0.3.
(3) Heating the precursor to 550 ℃ at the heating rate of 5 ℃/min under the protection of argon, and preserving heat for 3 hours to obtain the Co2P/C composite material.
For Co prepared in this example2The P/C composite material adopts a Scanning Electron Microscope (SEM) to carry out appearance structure characterization, adopts a full-automatic multifunctional gas adsorption instrument to carry out pore structure characterization, and has the following results.
Co prepared in this example2The P/C composite material comprises a carbon material substrate and monodisperse Co embedded in the carbon material substrate2P nanosheet, carbon material substrate and Co2The mass ratio of the P nano sheets is 0.25: 1; the Co2The size of the P nano sheet is 1-3 mu m, and the thickness is 3-11 nm; the Co2The P/C composite material is a porous material with a laminated structure, and the specific surface area of the P/C composite material is 256m2g-1The porosity is 50%, and the pore diameter is 1-4 nm.
Co prepared in this example2The electrochemical performance test results of the P/C composite material are shown in Table 1 and Table 2.
FIG. 1 shows Co prepared in this example2X-ray powder diffraction (XRD) pattern of P/C composite material, which indicates that the obtained product is pure Co2The position of the diffraction peak of P is matched with the JCPDS No.32-0306 standard map, no other impurity phase exists, and the crystallinity is high.
FIG. 2 shows Co prepared in this example2SEM image of P/C composite material, and analysis of the image shows that the product Co2The P/C has a layered structure, the size of the nanosheet is 1-3 mu m, and the thickness is 3-11 nm.
FIG. 3 shows Co prepared in this example2The P/C composite material is used as a cycle performance test chart of the sodium ion battery cathode material (the specific method for preparing the sodium ion battery refers to an electrochemical performance test part) under the conditions that the voltage interval is 0.01-3.0V and the current density is 50mA/g, and the chart shows that the current density of 50mA/g is 0.01-3.0V at 25 DEG CCharge-discharge cycles were conducted, and Co prepared in this example2The P/C composite material has the first discharge capacity of 783.5mAh/g, the charge capacity of 586.7mAh/g, and the reversible specific capacity of 463.8mAh/g after 50 circles, and shows excellent cycling stability.
Example 2
This example prepares Co as follows2P/C composite material:
(1) 0.6112g of Co (NO)3)2·6H2O, 0.2927g of red phosphorus and 0.1g of CTAB surfactant were added to 35mL of deionized water and magnetically stirred. Transferring the obtained suspension into a stainless steel autoclave with a 50mL Teflon lining, placing the stainless steel autoclave in an oven at 150 ℃, and reacting for 60 hours to obtain Co2And (3) P precursor. Then washing with 2mol/L hydrochloric acid twice, washing with deionized water and alcohol several times, and drying in a drying oven.
Wherein, Co (NO)3)2·6H2The molar ratio of O to red phosphorus is 1:4.5, and the concentration of a surfactant (CTAB) in a suspension system used for the hydrothermal reaction is 2.85 g/L.
(2) Then 1g of dried Co was taken2Adding the P precursor into 0.04mol/L glucose solution, transferring into a stainless steel autoclave with a 50mL Teflon lining, placing the stainless steel autoclave in an oven at 190 ℃, and reacting for 4 hours to obtain Co2P/C composite material precursor.
Wherein said Co2The mass ratio of the P precursor to the organic carbon source (glucose) was 1: 0.25.
(3) Mixing Co2And under the protection of argon, heating the precursor of the P/C composite material to 600 ℃ at the heating rate of 3 ℃/min, and preserving the heat for 2 hours to obtain the Co2P/C composite material.
The structure was characterized according to the method of example 1, and the result was Co prepared in this example2The P/C composite material comprises a carbon material substrate and monodisperse Co embedded in the carbon material substrate2P nanosheet, carbon material substrate and Co2The mass ratio of the P nano sheets is 0.2: 1; the Co2The size of the P nano-sheet is 2-4 μm, and the thickness is 5-10 nm; the Co2The P/C composite material is a porous material with a laminated structure, and the ratio of the porous material to the porous materialSurface area of 252m2g-1The porosity is 60%, and the pore diameter is 2-5 nm.
Co prepared in this example2The electrochemical performance test results of the P/C composite material are shown in Table 1 and Table 2.
FIG. 4 shows Co prepared in this example2The P/C composite material is used as a cycle performance test chart of a potassium ion battery cathode material (a specific method for preparing the potassium ion battery refers to an electrochemical performance test part) under the conditions that the voltage interval is 0.01-3.0V and the current density is 50mA/g, and the chart shows that at 25 ℃, the charge-discharge cycle is carried out at the current density of 50mA/g between 0.01-3.0V, and Co is subjected to Co-Co2The P/C composite material has the first discharge capacity of 627.9mAh/g, the charge capacity of 473.5mAh/g and the reversible specific capacity of 374.4mAh/g after 50 circles, and shows excellent circulation stability.
Example 3
This example prepares Co as follows2P/C composite material:
(1) 0.6112g of Co (NO)3)2·6H2O, 0.3902g of red phosphorus and 0.15g of SDBS surfactant were added to 35mL of deionized water and magnetically stirred. Transferring the obtained suspension into a stainless steel autoclave with a 50mL Teflon lining, placing the stainless steel autoclave in an oven at 220 ℃, and reacting for 30h to obtain Co2And (3) P precursor. Then washing with 1mol/L hydrochloric acid twice, washing with deionized water and alcohol several times, and drying in a drying oven.
Wherein, Co (NO)3)2·6H2The molar ratio of O to red phosphorus was 1:6, and the concentration of a surfactant (SDBS) in the suspension system used in the hydrothermal reaction was 4.29 g/L.
(2) Then 1g of dried Co was taken2Adding the P precursor into 0.08mol/L glucose solution, transferring the solution into a stainless steel autoclave with a 50mL Teflon lining, putting the stainless steel autoclave in an oven at 200 ℃, and reacting for 2 hours to obtain Co2P/C composite material precursor.
Wherein said Co2The mass ratio of the P precursor to the organic carbon source (glucose) was 1: 0.55.
(3) Mixing Co2P/C composite material precursorRaising the temperature to 700 ℃ at a heating rate of 10 ℃/min under the protection of argon, and preserving the temperature for 3 hours to obtain the Co2P/C composite material.
The structure was characterized according to the method of example 1, and the result was Co prepared in this example2The P/C composite material comprises a carbon material substrate and monodisperse Co embedded in the carbon material substrate2P nanosheet, carbon material substrate and Co2The mass ratio of the P nano-sheets is 0.47: 1; the Co2The size of the P nano sheet is 3-6 mu m, and the thickness is 6-14 nm; the Co2The P/C composite material is a porous material with a laminated structure, and the specific surface area of the P/C composite material is 249m2g-1The porosity is 60%, and the pore diameter is 3-10 nm.
Co prepared in this example2The electrochemical performance test results of the P/C composite material are shown in Table 1 and Table 2.
Example 4
This example prepares Co as follows2P/C composite material:
(1) 0.6112g of Co (NO)3)2·6H2O, 0.3252g of red phosphorus, and 0.14g of PVP surfactant were added to 35mL of deionized water and stirred magnetically. Transferring the obtained suspension into a 50mL stainless steel autoclave with a Teflon lining, placing the stainless steel autoclave in an oven at 170 ℃, and reacting for 48 hours to obtain Co2P precursor. Then washing with 3mol/L hydrochloric acid twice, washing with deionized water and alcohol several times, and drying in a drying oven.
Wherein, Co (NO)3)2·6H2The molar ratio of O to red phosphorus was 1:5, and the concentration of the surfactant (PVP) in the suspension system used for the hydrothermal reaction was 4 g/L.
(2) Then 1g of dried Co was taken2Adding the P precursor into 0.06mol/L glucose solution, transferring into a stainless steel autoclave with a 50mL Teflon lining, placing the stainless steel autoclave in an oven at 180 ℃, and reacting for 5 hours to obtain Co2P/C composite material precursor.
Wherein said Co2The mass ratio of the P precursor to the organic carbon source (glucose) was 1: 0.4.
(3) Mixing Co2P/C composite material precursor inRaising the temperature to 650 ℃ at the heating rate of 10 ℃/min under the protection of argon, and preserving the temperature for 4 hours to obtain the Co2P/C composite material.
The structure was characterized according to the method of example 1, and the result was Co prepared in this example2The P/C composite material comprises a carbon material substrate and monodisperse Co embedded in the carbon material substrate2P nanosheet, carbon material substrate and Co2The mass ratio of the P nano-sheets is 0.32: 1; the Co2The size of the P nano sheet is 1-4 mu m, and the thickness is 3-14 nm; the Co2The P/C composite material is a porous material with a laminated structure, and the specific surface area of the P/C composite material is 247m2g-1The porosity is 30%, and the pore diameter is 2-5 nm.
Co prepared in this example2The electrochemical performance test results of the P/C composite material are shown in Table 1 and Table 2.
Example 5
This example prepares Co as follows2P/C composite material:
(1) adding CoCl2·6H2O, red phosphorus and CTAB surfactant were added to 35mL of deionized water and stirred magnetically. Transferring the obtained suspension into a stainless steel autoclave with a 50mL Teflon lining, placing the stainless steel autoclave in an oven at 140 ℃, and reacting for 15h to obtain Co2And (3) P precursor. Then washing with 3mol/L hydrochloric acid twice, washing with deionized water and alcohol several times, and drying in a drying oven.
Wherein, CoCl2·6H2The molar ratio of O to red phosphorus was about 1:5.5, and the concentration of a surfactant (CTAB) in the suspension system used for the hydrothermal reaction was 3 g/L.
(2) Then 1g of dried Co was taken2Adding the P precursor into 0.03mol/L sucrose solution, transferring the solution into a 50mL stainless steel autoclave with a Teflon lining, putting the stainless steel autoclave in an oven at 160 ℃, and reacting for 5 hours to obtain Co2P/C composite material precursor.
Wherein said Co2The mass ratio of the P precursor to the organic carbon source (sucrose) is 1: 0.15.
(3) Heating the precursor to 500 ℃ at the heating rate of 1 ℃/min under the protection of argon, and preserving the temperature for 6 hours to obtain the Co2P/C composite material.
The structure was characterized according to the method of example 1, and the result was Co prepared in this example2The P/C composite material comprises a carbon material substrate and monodisperse Co embedded in the carbon material substrate2P nanosheet, carbon material substrate and Co2The mass ratio of the P nano-sheets is 0.14: 1; the Co2The size of the P nano sheet is 2-6 mu m, and the thickness is 3-7 nm; the Co2The P/C composite material is a porous material with a laminated structure, and the specific surface area of the P/C composite material is 257m2g-1The porosity is 40%, and the pore diameter is 3-6 nm.
Co prepared in this example2The electrochemical performance test results of the P/C composite material are shown in Table 1 and Table 2.
Comparative example 1
Comparative example preparation of Co2The P/C composite material was prepared by the method described in example 1, except that in the step (2), the dried Co was directly subjected to hydrothermal reaction2And (4) calcining the precursor obtained after mixing the precursor P with the glucose solution in the step (3), namely directly calcining the coated carbon without carrying out a second hydrothermal reaction.
Co prepared by the method of this comparative example2The P/C composite material has a disadvantage in that the uneven coating of the carbon layer affects the ion transport.
Co prepared in this comparative example2The electrochemical performance test results of the P/C composite material are shown in Table 1 and Table 2.
Comparative example 2
The method for preparing an anode material was as described in example 1 except that the Co obtained in step (1) was directly added without performing the operation of step (2)2And (4) carrying out the calcination operation of the step (3) on the P precursor.
The negative electrode material prepared in the comparative example was Co2P, without a carbon material substrate, the negative electrode material of this comparative example has a disadvantage in that the material conductivity is low, hindering the diffusion rate of ions, relative to the negative electrode material of the example.
The results of the electrochemical performance test of the anode material prepared in this comparative example are shown in tables 1 and 2.
Electrochemical performance test
And testing the conductivity by adopting a four-probe resistivity tester.
The products prepared in each example and comparative example were fabricated into sodium ion batteries or potassium ion batteries for performance testing.
The method for manufacturing the sodium-ion battery comprises the following steps: weighing 0.21g of the product prepared in the example or the comparative example, adding 0.06g of acetylene black as a conductive agent and 0.03g of polyvinylidene fluoride (PVDF) as a binder, fully grinding, adding a proper amount of N-methyl-pyrrolidone (NMP) solvent, uniformly mixing, coating on copper foil, drying in vacuum, punching into a round negative plate, taking a metal sodium plate as a counter electrode, taking an electrolyte of 1M NaClO4/DEC/EC (the mol ratio of DEC to EC is 1: 1), taking a diaphragm of Whatman glass fiber, and assembling into a CR2032 button cell in a glove box filled with argon.
The method for manufacturing the potassium ion battery comprises the following steps: weighing 0.28g of the product prepared in the example or the comparative example, adding 0.12g of acetylene black as a conductive agent and 0.04g of polyvinylidene fluoride (PVDF) as a binder, fully grinding, adding a proper amount of N-methyl-pyrrolidone (NMP) solvent, uniformly mixing, coating on copper foil, drying in vacuum, punching into a round negative plate, taking a metal potassium plate as a counter electrode, an electrolyte of 1M KPF6/DEC/EC (the mol ratio of DEC to EC is 1: 1), and a diaphragm of Whatman glass fiber, and assembling into a CR2032 button cell in a glove box filled with argon.
A Wuhan blue battery test system is adopted to carry out charge-discharge circulation at 25 ℃ and with the current density of 50mA/g between 0.01V and 3.0V, and the specific capacity and the circulation performance are tested. The results of the electrochemical performance tests are shown in tables 1 and 2.
Table 1 test results of sodium ion battery prepared
Table 2 test results of potassium ion battery prepared
It can be seen from the above examples and comparative examples that the cobalt phosphide/carbon composite material obtained by the method of twice hydrothermal treatment has unique structure and Co content2The P nanosheets are embedded into the carbon material substrate, so that the problem of volume change generated in the process of ion intercalation and deintercalation of phosphide particles is solved, and the circulation stability of the composite material is improved; on the other hand, the synergistic effect between carbon and phosphide improves the specific capacity and rate capability of the composite material. The unique result ensures that the cobaltous phosphide/carbon composite material provided by the invention has good conductivity, high specific capacity, good rate capability and cycle performance, and is particularly suitable for being used as a negative electrode material for sodium ion batteries or potassium ion batteries. The comparative example did not adopt the scheme of the present invention, and thus the excellent effects of the present invention could not be obtained.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (36)
1. A cobaltous phosphide/carbon composite material, comprising a carbon material substrate and Co embedded in the carbon material substrate2P nanosheet;
the cobalt phosphide/carbon composite material is prepared according to the following method, and the method comprises the following steps:
(1) mixing a cobalt source, a phosphorus source, a surfactant and water, and carrying out hydrothermal reaction to obtain Co2P precursor;
(2) mixing the Co of step (1)2Mixing the P precursor with an organic carbon source solution, and carrying out hydrothermal reaction to obtain Co2A P/C composite material precursor;
(3) mixing the Co of the step (2)2And calcining the precursor of the P/C composite material in a protective atmosphere to obtain the cobaltous phosphide/carbon composite material.
2. The cobalt phosphide/carbon composite material of claim 1, wherein the Co is2The P nanosheet is monodisperse Co2P nano-sheet.
3. The cobalt phosphide/carbon composite material of claim 1, wherein the Co is2The size of the P nano sheet is 1-6 μm.
4. The cobalt phosphide/carbon composite material of claim 1, wherein the Co is2The thickness of the P nano sheet is 3-14 nm.
5. The cobalt phosphide/carbon composite material according to claim 1, wherein the cobalt phosphide/carbon composite material has a layered structure.
6. The cobalt phosphide/carbon composite material according to claim 1, wherein the cobalt phosphide/carbon composite material comprises a carbon material substrate and Co2The mass ratio of the P nano-sheets is 0.1:1-0.5: 1.
7. The cobalt phosphide/carbon composite material as set forth in claim 1, wherein the specific surface area of the cobalt phosphide/carbon composite material is 220-260m2g-1。
8. The cobalt phosphide/carbon composite material according to claim 1, wherein the cobalt phosphide/carbon composite material is a porous material.
9. The cobaltous phosphide/carbon composite material of claim 8, wherein the porosity of the cobaltous phosphide/carbon composite material is 30-60%.
10. The cobalt phosphide/carbon composite material according to claim 8, wherein the pore size of the cobalt phosphide/carbon composite material is 1 to 10 nm.
11. A process for the preparation of a cobaltous phosphide/carbon composite material as defined in any one of claims 1 to 10, which comprises the steps of:
(1) mixing a cobalt source, a phosphorus source, a surfactant and water, and carrying out hydrothermal reaction to obtain Co2P precursor;
(2) mixing the Co of step (1)2Mixing the P precursor with an organic carbon source solution, and carrying out hydrothermal reaction to obtain Co2A P/C composite material precursor;
(3) mixing the Co of the step (2)2And calcining the precursor of the P/C composite material in a protective atmosphere to obtain the cobaltous phosphide/carbon composite material.
12. The method according to claim 11, wherein the cobalt source in step (1) is a soluble cobalt salt.
13. The method of claim 12, wherein the soluble cobalt salt comprises any one of cobalt nitrate, cobalt acetate, or cobalt chloride, or a combination of at least two thereof.
14. The method according to claim 11, wherein the phosphorus source in step (1) is red phosphorus.
15. The method according to claim 11, wherein the molar ratio of the cobalt source to the phosphorus source in step (1) is 1:4.5 to 1: 6.0.
16. The method according to claim 11, wherein the surfactant in step (1) comprises any one or a combination of at least two of cetyltrimethylammonium bromide, polyvinylpyrrolidone or sodium dodecylbenzenesulfonate.
17. The preparation method according to claim 11, wherein the concentration of the surfactant in the hydrothermal reaction system in the step (1) is 1.43 to 4.29 g/L.
18. The method of claim 11, wherein the mixing in step (1) is performed by stirring.
19. The method as claimed in claim 11, wherein the hydrothermal reaction in step (1) is carried out at a temperature of 140-220 ℃.
20. The preparation method according to claim 11, wherein the hydrothermal reaction time in step (1) is 15-60 h.
21. The method of claim 11, wherein the hydrothermal reaction of step (1) is carried out in a teflon-lined stainless steel autoclave.
22. The method of claim 11, wherein step (1) further comprises: to the Co2And washing and drying the P precursor.
23. The method of claim 22, wherein the washing step comprises washing with hydrochloric acid and then with water and ethanol.
24. The method according to claim 23, wherein the hydrochloric acid has a concentration of 1 to 3 mol/L.
25. The method according to claim 11, wherein in the step (2), the organic carbon source comprises any one of glucose, sucrose or citric acid or a combination of at least two thereof.
26. The method according to claim 11, wherein the concentration of the organic carbon source in the organic carbon source solution in the step (2) is 0.05 to 0.5 mol/L.
27. The method according to claim 11, wherein in the step (2), the Co is added2The mass ratio of the P precursor to the organic carbon source is 1:0.15-1: 0.55.
28. The method as claimed in claim 11, wherein the temperature of the hydrothermal reaction in step (2) is 160-200 ℃.
29. The preparation method according to claim 11, wherein the hydrothermal reaction time in the step (2) is 2-5 h.
30. The method of claim 11, wherein the hydrothermal reaction of step (2) is carried out in a teflon-lined stainless steel autoclave.
31. The method of claim 11, wherein the protective atmosphere of step (3) comprises argon.
32. The method as claimed in claim 11, wherein the temperature of the calcination in step (3) is 500-700 ℃.
33. The method of claim 11, wherein the calcination time in step (3) is 2-6 h.
34. The method of claim 11, wherein the temperature increase rate of the calcination in the step (3) is 1-10 ℃/min.
35. The method for preparing according to claim 11, characterized in that it comprises the steps of:
(1) mixing soluble cobalt salt, red phosphorus, a surfactant and water, carrying out hydrothermal reaction in a stainless steel autoclave with a Teflon lining at the temperature of 140-2P precursor;
wherein the molar ratio of the soluble cobalt salt to the red phosphorus is 1:4.5-1: 6.0; in the hydrothermal reaction system, the concentration of the surfactant is 1.43-4.29 g/L;
(2) mixing the Co of step (1)2Mixing the P precursor with 0.05-0.5mol/L organic carbon source solution, and then carrying out hydrothermal reaction in a stainless steel high-pressure kettle with a Teflon lining, wherein the temperature of the hydrothermal reaction is 160-200 ℃, and the time of the hydrothermal reaction is 2-5h, so as to obtain Co2A P/C composite material precursor;
wherein said Co2The mass ratio of the P precursor to the organic carbon source is 1:0.15-1: 0.55;
(3) mixing the Co of the step (2)2And heating the precursor of the P/C composite material to 500-700 ℃ at the heating rate of 1-10 ℃/min in the argon atmosphere for calcining for 2-6h to obtain the cobaltous phosphide/carbon composite material.
36. Use of a cobaltous phosphide/carbon composite material as defined in any one of claims 1 to 10 as a negative electrode material for sodium-ion batteries or potassium-ion batteries.
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