CN113479858A - Composite material for high-performance alkali metal ion battery cathode - Google Patents
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Abstract
The invention belongs to the technical field of electrochemical materials, and relates to a composite material for a high-performance alkali metal ion battery cathode, which is an amorphous BiPO containing oxygen vacancies4The nitrogen-doped carbon composite material has a microscopic morphology of nano spherical particles with a size range of 0.2-1.0 um, wherein BiPO4The mass fraction of the composite material is more than or equal to 60 percent, and the composite material can be used for alkali metal ion batteries and can perform reversible electrochemical conversion reaction and alloying reaction with alkali metal ionsThe specific capacity and the safety performance of the alkali metal ion battery are improved, and the oxygen anions can be used as a matrix for buffering volume change, so that electrode materials are prevented from being pulverized, and the cycle life is prolonged.
Description
The technical field is as follows:
the invention belongs to the technical field of electrochemical materials, and relates to a composite material for a high-performance alkali metal ion battery cathode, which improves the electrochemical performance by adjusting the oxygen vacancy concentration and the amorphous structure of the composite material.
Background art:
in recent years, with the increase of environmental pressure and traditional energy crisis, the proportion of electrochemical energy storage in energy structures is increasing due to lower environmental pollution and higher energy conversion rate. Among various electrochemical energy storage systems, alkali metal ion batteries (such as lithium ion batteries, sodium ion batteries and potassium ion batteries) are widely concerned due to the advantages of high mass/volume density, long service life, small environmental impact, flexible use, convenient maintenance and the like, and are suitable for various application scenes such as portable electronic equipment, electric automobiles, large-scale power grid energy storage and the like.
Among the electrode materials studied so far, alloy materials (such as Sn, Sb, Bi) are considered as a new generation of high energy density anode material to replace carbon anode materials due to their advantages of high theoretical specific capacity, suitable voltage plateau, etc. However, the large volume deformation of the alloy material during cycling causes the active material to be crushed and subsequently peeled off from the current collector, thereby causing the formation of interfacial layers of the solid electrolyte repeatedly, directly resulting in capacity fade and poor cycle performance. Alloy-based phosphates have not gained much attention as compared to widely studied carbon materials, alloy-based oxides and sulfides, but this does not mean that it is not worth further investigation. For example, BiPO4Polyanion group (PO) of (III)4) The structural deformation in the circulation process can be stabilized, so that the circulation stability of the electrode material is improved, but the poor intrinsic conductivity of the electrode material greatly limits the further application of the material in the field of energy storage.
Researches show that oxygen vacancies are introduced into an oxide or phosphate electrode material to provide additional reaction sites, enhance the electronic conductivity, promote the ion transmission and deform a buffer structure, thereby greatly improving the electrode performance. There are many methods for controlling the formation of oxygen vacancies, such as ion doping, high energy particle bombardment, plasma induction, and the like. These conventional methods introduce oxygen vacancies by post-treatment based on the synthesis of vacancy-free materials, require multi-step processes and complicated devices, and are not suitable for practical applications. Therefore, how to realize the controllable adjustment of the vacancy structure by using a simple method is still a key problem to be solved urgently for adjusting the material performance by using the vacancy.
Due to the special isotropic property and the efficient seepage path of the amorphous material, the diffusion rate of alkali metal ions in the electrode and the electrolyte can be improved. Studies show that Li+And Na+Diffusion in amorphous materials is sometimes faster than diffusion in crystalline materials of similar particle size and morphology, however no study has been reported in the prior art as to whether amorphous materials have an effect on potassium storage properties. Furthermore, it is not clear whether the engineering of oxygen vacancies and the cooperative interface of amorphous structures can be synthesized by a simple method.
The invention content is as follows:
aiming at the defects in the prior art, the invention designs and provides a composite material for a high-performance alkali metal ion battery cathode, which is prepared by one step by adopting a method of high-temperature carbonization of bismuth salt and a phosphorus-containing organic matter.
In order to achieve the aim, the composite material for the cathode of the high-performance alkali metal ion battery is amorphous BiPO containing oxygen vacancies4The nitrogen-doped carbon composite material has a microscopic morphology of nano spherical particles with a size range of 0.2-1.0 um, wherein BiPO4The mass fraction is more than or equal to 60 percent.
The process for preparing the high-performance alkali metal ion battery cathode composite material specifically comprises the following steps:
(1) firstly, grinding bismuth salt and organic phosphoric acid in a glove box filled with argon for 15 minutes, and then calcining at high temperature in a tubular furnace;
(2) will step withDissolving the calcined product in the step (1) in an ethanol solution, performing ultrasonic treatment for 30 minutes, performing suction filtration, washing and drying to obtain the high-performance alkali metal ion battery cathode BiPO4A nitrogen-doped carbon composite material.
Preferably, the bismuth source in the step (1) is bismuth nitrate; the organic phosphoric acid is one of ethylenediamine tetra methylene phosphonic acid, ammonium dihydrogen phosphate, phenylphosphonic acid, diphenyl phosphoric acid and triphenyl phosphonic acid.
Preferably, the molar ratio of bismuth to phosphorus in the reactant in the step (1) is 1: 3-1: 6.
Preferably, the calcining atmosphere in the step (1) is H2Mixed gas of/Ar (wherein H2The volume ratio of Ar to Ar is 0.05-0.1: 1.
preferably, the high-temperature calcination in the step (1) is carried out at a temperature of 400-500 ℃ for 1-6 hours.
The composite material for the cathode of the high-performance alkali metal ion battery can be used for lithium ion batteries, sodium ion batteries and potassium ion batteries.
Compared with the prior art, the invention has the following beneficial effects:
(1) the composite material can perform reversible electrochemical conversion reaction and alloying reaction with alkali metal ions, has high specific capacity and safety performance, and can prevent electrode material from being pulverized by taking oxyanions as a matrix for buffering volume change, thereby prolonging the cycle life.
(2) The composite material is prepared by mixing H2the/Ar mixed gas replaces high-purity Ar to serve as annealing atmosphere, the concentration of oxygen vacancies in the composite material is obviously improved, the existence of the oxygen vacancies provides additional reaction sites, the electronic conductivity is enhanced, the ion transmission is promoted, and the structural deformation is relieved, so that the electrode performance is greatly improved, and the diffusion rate of alkali metal ions in the electrode and the electrolyte can be improved due to the amorphous structure of the composite material.
(3) The composite material has excellent specific capacity, cycle performance and rate capability in alkali metal ion batteries, particularly potassium ion batteries, and simultaneously shows good rate and cycle performance under the conditions of large current charge and discharge, and the rate and cycle performance are 0.1Ag-1、0.2Ag-1、0.5Ag-1、1.0Ag-1、2.0Ag-1、5.0Ag-1、10.0Ag-1The specific capacity respectively reaches 292.4mAh g under the current density of-1,254.9mAh g-1,209.8mAh g-1,178.0mAh g-1,147.6mAh g-1,104.5mAh g-1、82.5mAh g-1(ii) a At 0.5Ah g-1The current density of the alloy can be kept at 250.6mAh g after circulating for 2000 circles-1Specific capacity of (a); the method provides a new choice for the cathode material applicable to alkali metal ion batteries, particularly potassium ion batteries, lays a foundation for possible high-current charge and discharge applications, and is hopeful to be applied in the fields of electric vehicles and the like requiring high-current charge and discharge on a large scale.
Description of the drawings:
fig. 1 is an XRD spectrum of the samples prepared in example 1, comparative example 1, and comparative example 2.
FIG. 2 is A-OV-BiPO prepared in example 14Scanning electron microscope images of/NC composite materials.
FIG. 3 is an EPR spectrum of the samples prepared in example 1, comparative example 1 and comparative example 2.
Fig. 4 is a graph of electrochemical rate performance of the potassium ion battery of the three electrode materials in experimental example 1.
Fig. 5 is a graph of electrochemical cycling performance of the potassium ion battery of the three composites of test example 1.
Fig. 6 is a graph of electrochemical rate performance of lithium ion batteries of the three composite materials in experimental example 2.
Fig. 7 is a graph of electrochemical cycle performance of lithium ion batteries of the three composites in experimental example 2.
Fig. 8 is a graph of electrochemical rate performance of sodium ion batteries of the three composites in experimental example 3.
Fig. 9 is a graph of electrochemical cycling performance of sodium ion batteries of the three composites of experimental example 3.
The specific implementation mode is as follows:
the present invention will be further described with reference to the following examples, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1:
the composite material for the negative electrode of the high-performance alkali metal ion battery is marked as A-OV-BiPO4The specific preparation process comprises the following steps:
(1) 0.485g of Bi (NO)3)3·5H2O and 0.545g of ethylenediaminetetramethylenephosphonic acid (EDTMPA) were ground for 15 minutes in a glove box filled with argon, and the resulting ground product was placed in H2/Ar (wherein H2The volume ratio of Ar to Ar is 0.05-0.1: 1) calcining the mixture for 2 hours in an atmosphere tube furnace at the temperature rising rate of 2 ℃ per minute to 400 ℃;
(2) dissolving the calcined product in the step (1) in an ethanol solution, performing ultrasonic treatment for 30 minutes, then performing suction filtration and washing for three times by using water and ethanol respectively, and drying the obtained product in a vacuum drying oven at 60 ℃ for 12 hours to obtain BiPO with an amorphous structure and rich oxygen vacancies4the/NC composite material is A-OV-BiPO4/NC。
Comparative example 1:
the composite material for the negative electrode of the alkali metal ion battery in the comparative example is marked as C-OV-BiPO4The preparation process of the/NC-1 comprises the following steps:
(1) 0.485g of Bi (NO)3)3·5H2O and 0.545g of ethylenediamine tetramethylene phosphonic acid (EDTMPA) were ground in a glove box filled with argon for 15 minutes, and then the resulting ground product was calcined in a tube furnace under a high-purity argon atmosphere at a temperature rising rate of 2 ℃ per minute to 400 ℃ for 2 hours;
(2) dissolving the calcined product in the step (1) in an ethanol solution, performing ultrasonic treatment for 30 minutes, then performing suction filtration and washing for three times by using water and ethanol respectively, and drying the obtained product in a vacuum drying oven at 60 ℃ for 12 hours to prepare BiPO with good crystallinity and low oxygen vacancy content4the/NC composite material is C-OV-BiPO4/NC-1。
Comparative example 2:
base as in this comparative exampleThe composite material for the metal ion battery negative electrode is marked as C-OV-BiPO4The preparation process of the/NC-2 comprises the following steps:
(1) A-OV-BiPO prepared in example 14Placing the NC material in a tubular furnace in a high-purity argon atmosphere to be calcined for 2 hours at the temperature rise rate of 2 ℃ per minute to 400 ℃, and preparing BiPO with good crystallinity and high oxygen vacancy content4(ii) a/NC composite material, namely as C-OV-BiPO4/NC-2。
A-OV-BiPO prepared in example 14(NC) composite, C-OV-BiPO prepared in comparative example 14(NC-1) composite, C-OV-BiPO prepared in comparative example 24The XRD spectrum of the/NC-2 composite material is shown in figure 1, and the prepared A-OV-BiPO can be known from figure 14the/NC sample is amorphous structure, while C-OV-BiPO4/NC-1、C-OV-BiPO4the/NC-2 sample had good crystallinity.
A-OV-BiPO prepared in example 14SEM image of/NC composite As shown in FIG. 2, it can be seen from FIG. 2 that A-OV-BiPO was prepared4The spherical shape of the/NC sample.
A-OV-BiPO prepared in example 14(NC) composite, C-OV-BiPO prepared in comparative example 14(NC-1) composite, C-OV-BiPO prepared in comparative example 24The Electron Paramagnetic Resonance (EPR) spectrum of the/NC-2 composite material is shown in FIG. 3, and it can be seen from FIG. 3 that 3 samples prepared all contain oxygen vacancies and A-OV-BiPO4The oxygen vacancy content of the/NC composite material is higher.
Test example 1:
this test example A-OV-BiPO prepared in example 1 was used4C-OV-BiPO prepared in comparative example 1/NC4C-OV-BiPO prepared according to/NC-1 and comparative example 24The method is characterized in that the/NC-2 is applied to the research of the potassium ion battery cathode to test the electrochemical performance of the potassium ion battery cathode, and comprises the following specific steps:
respectively taking A-OV-BiPO4/NC、C-OV-BiPO4(iv) NC-1 and C-OV-BiPO4(NC-2) as an active material, acetylene black: sodium carboxymethylcellulose: mixing the active substances according to the ratio of 15:15:70, adding deionized water to prepare slurry, controlling a certain thickness, and uniformly coating the slurry on a copper foil current collectorThen cutting the mixture into 12mm electrode plates, drying the electrode plates for 12 hours at 80 ℃ in vacuum, assembling the battery into a button cell (CR2032) in a glove box by taking a potassium plate as a counter electrode, glass fiber filter paper as a diaphragm and 1.0M KFSI ineC: DEC (1:1) as the electrolyte of the battery, wherein the working interval of the battery is 0.01V-3.0V.
For using A-OV-BiPO4/NC、C-OV-BiPO4(iv) NC-1 and C-OV-BiPO4The button cell assembled by/NC-2 is subjected to rate performance test, the result is shown in figure 4, and A-OV-BiPO is adopted4The button cell assembled by/NC is 0.1Ag-1、0.2Ag-1、0.5Ag-1、1.0Ag-1、2.0Ag-1、5.0Ag-1、10.0Ag-1The specific capacity respectively reaches 292.4mAh g under the current density of-1,254.9mAh g-1,209.8mAh g-1,178.0mAh g-1,147.6mAh g-1,104.5mAh g-1、82.5mAh g-1Higher than C-OV-BiPO4/NC-1，C-OV-BiPO4The performance of/NC-2, from which it can be seen that A-OV-BiPO was used4the/NC has better rate performance when used as the negative electrode of the potassium ion battery.
By adopting A-OV-BiPO4The cycling performance of a button cell assembled from/NC at 500mA g is shown in FIG. 5-1The current density of the alloy can be respectively kept at 250.6mAh g after being circulated for 2000 circles-1The specific capacity of (A).
Test example 2:
this test example A-OV-BiPO prepared in example 1 was used4C-OV-BiPO prepared in comparative example 1/NC4C-OV-BiPO prepared according to/NC-1 and comparative example 24The method is characterized in that the/NC-2 is applied to the research of the lithium ion battery cathode to test the electrochemical performance, and comprises the following specific steps:
respectively taking A-OV-BiPO4/NC、C-OV-BiPO4(iv) NC-1 and C-OV-BiPO4(NC-2) as an active material, acetylene black: sodium carboxymethylcellulose: mixing active substances at a ratio of 15:15:70, adding deionized water to prepare slurry, uniformly coating the slurry on a copper foil current collector with a certain thickness, cutting the copper foil current collector into 12mm electrode plates, drying the electrode plates for 12 hours at 80 ℃ in vacuum, taking a lithium plate as a counter electrode, and performing polyolefin porous treatmentThe film is a diaphragm and takes 1.0M LiFP6DEC ═ 1: 12% FEC was used as an electrolyte of the cell, and a button cell (CR2025) was assembled in a glove box, and the cell operating range was 0.01V to 3.0V.
For using A-OV-BiPO4/NC、C-OV-BiPO4(iv) NC-1 and C-OV-BiPO4The button cell assembled by/NC-2 is subjected to rate performance test, the result is shown in figure 7, and A-OV-BiPO is adopted4Button cell assembled by/NC is 0.1A g-1、0.2A g-1、0.5A g-1、1.0A g-1、2.0A g-1、5.0A g-1、10.0A g-1The specific capacity reaches 666.3mAh g respectively under the current density of-1,638.4mAh g-1,594.5mAh g-1,530.4mAh g-1,478.0mAh g-1,354.9mAh g-1、276.8mAh g-1Higher than C-OV-BiPO4/NC-1，C-OV-BiPO4The performance of/NC-2, from which it can be seen that A-OV-BiPO was used4the/NC has better rate performance when used as the cathode of the lithium ion battery.
By adopting A-OV-BiPO4The button cell assembled by the/NC is 1000mA g-1The cycle performance at a current density of (2) is shown in FIG. 5, at 1000mA g-1The current density of the alloy can be kept at 496.0mAh g after being circulated for 500 circles-1The specific capacity of (A).
Test example 3:
this test example A-OV-BiPO prepared in example 1 was used4C-OV-BiPO prepared in comparative examples 1 and 2/NC composite Material4/NC-1，C-OV-BiPO4the/NC-2 material is applied to the research of the negative electrode of the sodium-ion battery and tests the electrochemical performance of the negative electrode of the sodium-ion battery, and the specific steps are as follows:
respectively taking A-OV-BiPO4/NC、C-OV-BiPO4(iv) NC-1 and C-OV-BiPO4(NC-2) as an active material, acetylene black: sodium carboxymethylcellulose: the active substances are mixed according to the proportion of 15:15:70, deionized water is added to prepare slurry, and the slurry is uniformly coated on the copper foil current collector by controlling a certain thickness. Cutting into 12mm electrode pieces, drying at 80 deg.C for 12 hr, and assembling into button cell in glove box. Sodium sheet as counter electrode and glass fiber filter paper as filter paperMembrane with 1.0M NaClO4And the battery electrolyte solution of the battery is DMC 1: 12%, and the battery is assembled into a button battery (CR2032), wherein the working range of the battery is 0.01V-3.0V.
For using A-OV-BiPO4/NC、C-OV-BiPO4(iv) NC-1 and C-OV-BiPO4The button cell assembled by/NC-2 is subjected to rate performance test, the result is shown in figure 8, and A-OV-BiPO is adopted4Button cell assembled by/NC is 0.1A g-1、0.2A g-1、0.5A g-1、1.0A g-1、2.0A g-1、5.0A g-1、10.0A g-1The specific capacity respectively reaches 284.8mAh g under the current density of-1,254.3mAh g-1,218.1mAh g-1,205.4mAh g-1,180.4mAh g-1,139.5mAh g-1、112.6mAh g-1Higher than C-OV-BiPO4/NC-1，C-OV-BiPO4The performance of/NC-2, from which it can be seen that A-OV-BiPO was used4the/NC has better rate performance when being used as the cathode of the sodium-ion battery.
By adopting A-OV-BiPO4The button cell assembled by the/NC is 1000mA g-1The cycle performance at a current density of (2) is shown in FIG. 9, at 1000mA g-1Can maintain 201.1mAh g after circulating for 500 circles under the current density-1The specific capacity of (A).
Claims (6)
1. The composite material for the negative electrode of the high-performance alkali metal ion battery is characterized in that the composite material is amorphous BiPO containing oxygen vacancies4The nitrogen-doped carbon composite material has a microscopic morphology of nano spherical particles with a size range of 0.2-1.0 um, wherein BiPO4The mass fraction is more than or equal to 60 percent.
2. The composite material for the negative electrode of the high-performance alkali metal ion battery according to claim 1, wherein the process for preparing the composite material specifically comprises the following steps:
(1) firstly, grinding bismuth salt and organic phosphoric acid in a glove box filled with argon for 15 minutes, and then calcining at high temperature in a tubular furnace;
(2) after the step (1) is calcinedDissolving the product in ethanol solution, performing ultrasonic treatment for 30 minutes, performing suction filtration, washing and drying to obtain the high-performance alkali metal ion battery cathode BiPO4A nitrogen-doped carbon composite material.
3. The composite material for the negative electrode of the high-performance alkali metal ion battery according to claim 2, wherein the bismuth source in the step (1) is bismuth nitrate; the organic phosphoric acid is one of ethylenediamine tetra methylene phosphonic acid, ammonium dihydrogen phosphate, phenylphosphonic acid, diphenyl phosphoric acid and triphenyl phosphonic acid.
4. The composite material for the negative electrode of the high-performance alkali metal ion battery as claimed in claim 2, wherein the molar ratio of bismuth to phosphorus in the reactant in the step (1) is 1:3 to 1: 6.
5. The composite material for the negative electrode of the high-performance alkali metal ion battery according to claim 2, wherein the calcination atmosphere in the step (1) is H2Mixed gas of/Ar (wherein H2The volume ratio of Ar to Ar is 0.05-0.1: 1.
6. the composite material for the negative electrode of the high-performance alkali metal ion battery according to claim 2, wherein the high-temperature calcination in the step (1) is performed at a temperature of 400 to 500 ℃ for 1 to 6 hours.
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