Nitrogen-phosphorus-doped carbon composite iron phosphide three-dimensional rod-shaped porous material, lithium battery diaphragm and preparation method thereof, lithium-sulfur battery and electric equipment
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a nitrogen-phosphorus-doped carbon composite iron phosphide three-dimensional rod-shaped porous material, a lithium battery diaphragm, a preparation method of the lithium battery diaphragm, a lithium sulfur battery and electric equipment.
Background
The lithium-sulfur (Li-S) battery is an electrochemical energy storage system with sulfur as a positive electrode (theoretical specific capacity of 1675mAh/g) and lithium as a negative electrode (theoretical specific capacity of 3860mAh/g), and the sulfur positive electrode is low in price and environment-friendly. In recent years, lithium-sulfur batteries have been receiving increasing attention as an advanced lithium ion battery.
However, there are still a number of serious problems to be solved in lithium-sulfur batteries. For example, polysulfides generated during charge and discharge dissolve in the electrolyte and repeatedly diffuse between the positive and negative electrodes, i.e., a "shuttle effect" is generated. The shuttle effect can cause the discharge specific capacity of the lithium-sulfur battery to be reduced and the cycle performance to be poor. Therefore, how to inhibit the "shuttling effect" of polysulfide becomes a hot research focus for improving the battery performance of lithium-sulfur batteries.
The prior art mostly considers the problem of shuttle effect from the aspect of positive electrode performance, but the problem cannot be well solved by singly improving the positive electrode material.
In view of this, the present application is specifically made.
Disclosure of Invention
The invention aims to provide a nitrogen-phosphorus-doped carbon composite iron phosphide three-dimensional rod-shaped porous material, a lithium battery diaphragm, a preparation method of the lithium battery diaphragm, a lithium sulfur battery and electric equipment, so as to solve the problems.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a nitrogen-phosphorus-doped carbon composite iron phosphide three-dimensional rod-like porous material comprises the following steps:
mixing raw materials including an iron source, a nitrogen-containing organic matter, phytate and an organic solvent, and drying to obtain a precursor;
and heating the precursor to obtain the nitrogen-phosphorus-doped carbon composite iron phosphide three-dimensional rod-like porous material.
It should be noted that the organic solvent may be a common organic solvent, such as ethanol.
Preferably, the method for preparing the iron source comprises:
mixing raw materials including iron powder, 1,2, 3-trimesic acid, hydrofluoric acid, nitric acid and water, and carrying out hydrothermal reaction to obtain the iron source.
More preferably, the molar ratio of the iron powder, the 1,2, 3-trimesic acid, the hydrofluoric acid, the nitric acid and the water is (3-6): (2-4): (2-4): (5-10): (600-1000);
preferably, the temperature of the hydrothermal reaction is 160-200 ℃, and the time is 12-24 h;
preferably, the hydrothermal reaction further comprises, after the completion of the hydrothermal reaction:
the reaction product was washed sequentially with water, DMF and ethanol and then dried to obtain the iron source.
The purpose of washing the reaction product is mainly to remove reaction impurities and ensure that the obtained iron source is free from the influence of impurities when the nitrogen-phosphorus-doped carbon composite iron phosphide three-dimensional rod-shaped porous material is prepared.
Alternatively, the molar ratio of the iron powder, the 1,2, 3-trimesic acid, the hydrofluoric acid, the nitric acid, and the water may be (3-6): (2-4): (2-4): (5-10): (600-1000), such as 3:2:2: 5: 600. 6:4:4:10: 1000. 4:3:3: 6: 700. 5: 2.5: 3.5: 7: 800. 4.5: 3: 4: 8: 900, etc.; the temperature of the hydrothermal reaction can be any value between 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ and 160-200 ℃, and the time can be any value between 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h and 12-24 h.
Preferably, the nitrogen-containing organic substance comprises one or more of urea, ethylenediamine and dimethylamine;
preferably, the phytate comprises one or more of sodium phytate, potassium phytate and zinc phytate.
The sodium phytate, the potassium phytate and the zinc phytate are phosphorus sources which are very suitable for preparing the nitrogen-phosphorus-doped carbon composite iron phosphide three-dimensional rod-shaped porous material.
Preferably, the heat treatment specifically comprises: treating for 2-5h at the temperature of 700-900 ℃ in a protective atmosphere;
preferably, the heating rate of the heating treatment is 1-5 ℃/min;
preferably, the gas used for the protective atmosphere comprises nitrogen and/or argon;
preferably, the molar ratio of the iron source, the nitrogen-containing organic matter and the phytate is 1 (1-10): (1-5).
The temperature of the heat treatment can be any value between 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ and 700 and 900 ℃, and the treatment time can be any value between 2h, 3h, 4h, 5h and 2-5 h; the heating rate of the heating treatment can be any value between 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min and 1-5 ℃/min; the molar ratio of the iron source, the nitrogen-containing organic matter and the phytate can be 1 (1-10): (1-5), for example: 1: 1: 1. 1: 10: 5. 1: 2: 2. 1: 5: 3. 1: 10: 4, etc.
The nitrogen-phosphorus-doped carbon composite iron phosphide three-dimensional rod-shaped porous material is prepared by using the preparation method of the nitrogen-phosphorus-doped carbon composite iron phosphide three-dimensional rod-shaped porous material.
A method for preparing a lithium battery separator, comprising:
mixing raw materials including a nitrogen-phosphorus-doped carbon composite iron phosphide three-dimensional rod-shaped porous material, a binder and a solvent to obtain coating slurry;
coating the coating slurry on the surface of a diaphragm substrate to obtain the lithium battery diaphragm;
preferably, the binder comprises one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, sodium carboxymethylcellulose, and polyurethane;
preferably, the mass ratio of the nitrogen-phosphorus-doped carbon composite iron phosphide three-dimensional rod-like porous material to the binder is (6-8): (2-4);
preferably, the diaphragm base material comprises any one of a PP diaphragm base material, a PP/PE/PP diaphragm base material, a cellulose diaphragm base material, a non-woven fabric diaphragm base material and a PE diaphragm base material;
preferably, the thickness of the membrane substrate is 10-30 μm; the thickness of the coating is 2-10 μm;
more preferably, the thickness of the coating slurry is 5 μm.
Optionally, the mass ratio of the nitrogen-phosphorus-doped carbon composite iron phosphide three-dimensional rod-like porous material to the binder may be (6-8): (2-4), for example: 6: 2. 8: 4. 7:3, etc. The thickness of the separator substrate may be any value between 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, and 10-30 μm; the thickness of the coating slurry may be any value between 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, and 2-10 μm. The performance is best when the coating thickness is 5 μm.
The solvent may be selected from common organic solvents for preparing slurry, such as ethanol, and the application is not limited thereto.
A lithium battery diaphragm is prepared by the preparation method of the lithium battery diaphragm.
A lithium-sulfur battery comprises the lithium battery diaphragm.
An electric device comprises the lithium-sulfur battery.
Compared with the prior art, the invention has the beneficial effects that at least:
1. the nitrogen-phosphorus-doped carbon composite iron phosphide three-dimensional rod-shaped porous material and the lithium battery diaphragm belong to a nitrogen-phosphorus double-doped carbon and FeP composite three-dimensional rod-shaped porous structure, and have stronger polysulfide adsorption capacity due to the doping of two elements of nitrogen and phosphorus; meanwhile, the P functional group and sulfur have good interaction, so that the sulfur on the anode and the porous carbon doped with P can form strong interface coupling, polysulfide can be preferentially adsorbed on the carbon material, the diffusion of the polysulfide can be better prevented, and the shuttle effect of the polysulfide can be effectively inhibited; FeP has the function of accelerating the catalytic conversion of polysulfide, which is based on the fact that metal phosphide has a polysulfide diffusion energy barrier lower than that of metal oxide, so that compared with the traditional metal oxide/carbon composite coating, the metal phosphide/carbon composite coating is more suitable for modifying the diaphragm and effectively inhibiting the shuttle effect of polysulfide;
2. the preparation method of the nitrogen-phosphorus-doped carbon composite iron phosphide three-dimensional rod-shaped porous material and the lithium battery diaphragm, which are provided by the application, is simple in process and low in cost, and the prepared product is stable in performance.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope of the present invention.
FIG. 1 is an electron micrograph of an iron source material prepared in example 1;
FIG. 2 is an electron microscope image of the FeP @ NPC three-dimensional rod-like porous material prepared in example 1.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Weighing iron powder and 1,2, 3-trimesic acid, putting the iron powder and the 1,2, 3-trimesic acid into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, and adding hydrofluoric acid, nitric acid and pure water, wherein the molar ratio of each sample is n (iron powder): n (1, 2, 3-trimesic acid): n (HNO)3): n (HF): n (pure water) =3:2:2:7:800, after uniformly stirring, placing the hydrothermal reaction kettle at 160 ℃ for sealed reaction for 12 hours, naturally cooling to room temperature, respectively washing 3 times with deionized water, DMF and absolute ethyl alcohol, and drying in an oven to obtain the iron source A for later use.
FIG. 1 is an electron micrograph of an iron source material prepared in example 1 of the present invention.
Weighing 200mg of iron source A material, dissolving in 30 mL of ethanol solution, weighing 834 mg of sodium phytate and 60mg of urea, adding, stirring overnight, and drying in a vacuum drying oven at 60 ℃ to obtain the precursor material. Weighing a certain mass of precursor material, placing the precursor material in a square porcelain boat, and then annealing at 700 ℃ for 2 hours at a heating rate of 2 ℃/min in a nitrogen atmosphere to obtain FeP @ NPC. It is understood that FeP @ NPC denotes a complex of FeP and NPC.
FIG. 2 is an electron microscope image of a FeP @ NPC three-dimensional rod-like porous material prepared in example 1 of the present invention.
Uniformly mixing FeP @ NPC and a binder according to a mass ratio of 8:2, and then dispersing into an ethanol solvent; obtaining uniformly dispersed coating slurry through ultrasonic dispersion; and coating the obtained coating slurry on the surface of a diaphragm base material (PP/PE/PP diaphragm base material) with the thickness of 25 mu m, wherein the thickness of a coating obtained by the coating slurry is 2 mu m, and drying in vacuum to obtain the modified diaphragm for the lithium-sulfur battery.
The sulfur positive electrode, the modified diaphragm of the lithium-sulfur battery prepared in the example, the lithium negative electrode, and the organic electrolyte 1M LiTFSI (lithium bis (trifluoromethyl) sulfenamide) +0.1M LiNO3(lithium nitrate) + DOL (1, 3-dioxolane)/DME (ethylene glycol dimethyl ether) (1/1, v/v) in a glove box with a water oxygen content of less than 1ppmA lithium sulfur button cell was prepared with the designation D1.
Example 2
Weighing iron powder and 1,2, 3-trimesic acid, putting the iron powder and the 1,2, 3-trimesic acid into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, and adding hydrofluoric acid, nitric acid and pure water, wherein the molar ratio of each sample is n (iron powder): n (1, 2, 3-trimesic acid): n (HNO)3): n (HF): n (pure water) =6:4:4:10:1000, after uniformly stirring, placing the hydrothermal reaction kettle at 160 ℃ for sealed reaction for 12 hours, naturally cooling to room temperature, respectively washing with deionized water, DMF (dimethyl formamide) and absolute ethyl alcohol for 3 times, and drying in an oven to obtain the iron source A for later use.
Weighing 200mg of iron source A material, dissolving in 30 mL of ethanol solution, weighing 662 mg of potassium phytate and 90mg of ethylenediamine, adding, stirring overnight, and drying in a vacuum drying oven at 60 ℃ to obtain a precursor material. Weighing a certain mass of precursor material, placing the precursor material in a square porcelain boat, and then annealing at 800 ℃ for 3 hours at a heating rate of 3 ℃/min in a nitrogen atmosphere to obtain FeP @ NPC.
Uniformly mixing FeP @ NPC and a binder according to a mass ratio of 7:3, and then dispersing into an ethanol solvent; uniformly dispersed coating slurry is obtained through mechanical stirring; and coating the obtained coating slurry on the surface of a diaphragm base material (PE diaphragm base material) with the thickness of 25 micrometers, wherein the thickness of a coating obtained by the coating slurry is 5 micrometers, and performing vacuum drying to obtain the modified diaphragm for the lithium-sulfur battery.
The sulfur positive electrode, the modified diaphragm of the lithium-sulfur battery prepared in the example, the lithium negative electrode, and the organic electrolyte 1M LiTFSI (lithium bis (trifluoromethyl) sulfenamide) +0.1M LiNO3(lithium nitrate) + DOL (1, 3-dioxolane)/DME (ethylene glycol dimethyl ether) (1/1, v/v), a lithium sulfur button cell was prepared in a glove box with a water oxygen content of less than 1ppm, numbered D2.
Example 3
Weighing iron powder and 1,2, 3-trimesic acid, putting the iron powder and the 1,2, 3-trimesic acid into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, and adding hydrofluoric acid, nitric acid and pure water, wherein the molar ratio of each sample is n (iron powder): n (1, 2, 3-trimesic acid): n (HNO)3): n (HF): n (pure water) =4:3:3:5:600, stirring uniformly, and then placing the hydrothermal reaction kettle in a reactorAnd (3) placing the mixture at 160 ℃ for sealed reaction for 12h, naturally cooling the mixture to room temperature, respectively washing the mixture for 3 times by using deionized water, DMF (dimethyl formamide) and absolute ethyl alcohol, and drying the mixture in an oven to obtain the iron source A for later use.
Weighing 200mg of iron source A material, dissolving in 30 mL of ethanol solution, weighing 344 mg of zinc phytate and 120mg of dimethylamine, adding, stirring overnight, and drying in a vacuum drying oven at 60 ℃ to obtain a precursor material. Weighing a certain mass of precursor material, placing the precursor material in a square porcelain boat, and then annealing for 5 hours at 900 ℃ at the heating rate of 5 ℃/min in the argon atmosphere to obtain FeP @ NPC.
Uniformly mixing FeP @ NPC and a binder according to a mass ratio of 6:4, and then dispersing into an ethanol solvent; obtaining uniformly dispersed coating slurry through ultrasonic dispersion; coating the obtained coating slurry on the surface of a diaphragm base material (PP diaphragm base material) with the thickness of 25 mu m, wherein the thickness of a coating obtained by the coating slurry is 10 mu m; and (5) drying in vacuum to obtain the modified diaphragm for the lithium-sulfur battery.
The sulfur positive electrode, the modified diaphragm of the lithium-sulfur battery prepared in the example, the lithium negative electrode, and the organic electrolyte 1M LiTFSI (lithium bis (trifluoromethyl) sulfenamide) +0.1M LiNO3(lithium nitrate) + DOL (1, 3-dioxolane)/DME (ethylene glycol dimethyl ether) (1/1, v/v), a lithium sulfur button cell was prepared in a glove box with a water oxygen content of less than 1ppm, numbered D3.
Comparative example 1
A sulfur positive electrode, a common diaphragm (a single-layer PP film, a model of celgard2400, the thickness of 25 mu M), a lithium negative electrode, an organic electrolyte 1M LiTFSI (lithium bis (trifluoromethyl) sulfenamide) +0.1M LiNO3(lithium nitrate) + DOL (1, 3-dioxolane)/DME (ethylene glycol dimethyl ether) (1/1, v/v), a lithium sulfur button cell was prepared in a glove box with a water oxygen content of less than 1ppm, numbered D4.
Comparative example 2
Weighing 200mg of iron source A material, dissolving in 30 mL of ethanol solution, weighing 200mg of urea, adding, stirring overnight, drying in a vacuum drying oven at 60 ℃, washing with dilute hydrochloric acid to remove Fe element, alternately cleaning with ethanol and deionized water for 3 times, and drying in the vacuum drying oven at 60 ℃ to obtain the precursor material. Weighing a certain mass of precursor material, placing the precursor material in a square porcelain boat, and then annealing at 700 ℃ for 2 hours at a heating rate of 2 ℃/min in a nitrogen atmosphere to obtain NC.
Uniformly mixing NC and a binder according to a mass ratio of 6:4, and then dispersing into a solvent; uniformly dispersed coating slurry is obtained through mechanical stirring; and coating the obtained coating slurry on the surface of a diaphragm base material with the thickness of 25 microns, wherein the thickness of a coating prepared from the coating slurry is 5 microns, and drying in vacuum to obtain the modified diaphragm for the lithium-sulfur battery.
The sulfur positive electrode, the modified diaphragm of the lithium-sulfur battery prepared by the comparative example, the lithium negative electrode and the organic electrolyte of 1M LiTFSI (lithium bistrifluoromethylsulfonimide) +0.1M LiNO3(lithium nitrate) + DOL (1, 3-dioxolane)/DME (ethylene glycol dimethyl ether) (1/1, v/v), a lithium sulfur button cell was prepared in a glove box with a water oxygen content of less than 1ppm, numbered D5.
Comparative example 3
Weighing 200mg of iron source A material, dissolving in 30 mL of ethanol solution, weighing 140mg of ethylenediamine, adding, stirring overnight, and drying in a vacuum drying oven at 60 ℃ to obtain a precursor material. Weighing a certain mass of precursor material, placing the precursor material in a square porcelain boat, and then annealing at 700 ℃ for 2 hours at a heating rate of 2 ℃/min in a nitrogen atmosphere to obtain Fe3O4@NC。
Mixing Fe3O4Mixing the @ NC and the binder uniformly according to the mass ratio of 6:4, and then dispersing into a solvent; obtaining uniformly dispersed coating slurry through ultrasonic dispersion; and coating the obtained coating slurry on the surface of a diaphragm base material with the thickness of 25 microns, wherein the thickness of the coating is 5 microns, and drying in vacuum to obtain the modified diaphragm for the lithium-sulfur battery.
The sulfur positive electrode, the modified diaphragm of the lithium-sulfur battery prepared by the comparative example, the lithium negative electrode and the organic electrolyte of 1M LiTFSI (lithium bistrifluoromethylsulfonimide) +0.1M LiNO3(lithium nitrate) + DOL (1, 3-dioxolane)/DME (ethylene glycol dimethyl ether) (1/1, v/v), a lithium sulfur button cell was prepared in a glove box with a water oxygen content of less than 1ppm, numbered D6.
The discharge performance test is carried out on a D1-D6 battery sample at the temperature of 25 ℃, the voltage range of 1.7-2.8V and the temperature of 0.5C, and the results are shown in the following table 1:
TABLE 1D 1-D6 Voltage drop at 1.7-2.8V, 0.5C
|
0.5C specific first discharge capacity (mA h/g)
|
Specific capacity of 50 cycles discharge (mA h/g)
|
Capacity retention at 50 weeks
|
D1
|
945.1
|
870.4
|
92.10%
|
D2
|
950.7
|
882.7
|
92.84%
|
D3
|
945.6
|
867.7
|
91.76%
|
D4
|
941.2
|
816.8
|
86.78%
|
D5
|
943.8
|
835.1
|
88.48%
|
D6
|
942.6
|
842.8
|
89.41% |
As can be seen from table 1 above, the nitrogen-phosphorus-doped carbon composite iron phosphide three-dimensional rod-like porous material and the lithium ion battery prepared by using the membrane prepared by using the same have better electrochemical performance compared with the lithium ion battery prepared by using the existing pp membrane and the membrane which is not subjected to iron phosphide compounding, iron phosphide compounding and P doping.
The nitrogen-phosphorus double-doped carbon and FeP composite three-dimensional rod-shaped porous material, the prepared lithium ion battery diaphragm and the lithium ion battery can effectively inhibit the shuttle effect of polysulfide and improve the performance of the battery.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.