CN115101733A - (NiCo) Se/(NiCo) Se 2 @ C heterostructure composite material and preparation method and application thereof - Google Patents
(NiCo) Se/(NiCo) Se 2 @ C heterostructure composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses (NiCo) Se/(NiCo) Se 2 The method comprises the steps of adding nickel salt and cobalt salt into a mixed solution of glycerol and isopropanol to obtain a precursor, uniformly mixing the precursor with selenium powder, and then annealing to obtain (NiCo) Se 2 . Mixing (NiCo) Se 2 Ultrasonically dispersing into organic solution, and vigorously stirring to obtain (NiCo) Se 2 The @ organic composite material is then evenly mixed with selenium powder for the second time and then is annealed to prepare (NiCo) Se/(NiCo) Se 2 @ C heterostructure composite material. The heterostructure material obtained by the invention has good structural continuity and controllability, low product cost, environmental friendliness and reproducibilityThe performance is good. The material is used for the sodium ion battery, shows higher specific discharge capacity and good multiplying power and cycling stability, and has good implementation and development prospect.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and relates to (NiCo) Se/(NiCo) Se 2 The @ C heterostructure composite material and the preparation method and the application thereof.
Background
In recent years, Sodium Ion Batteries (SIBs) have attracted much attention because of their low cost and similar operating principles as Lithium Ion Batteries (LIBs). However, SIBs are due to Na, in contrast to LIBs + The large radius of (a) makes it difficult for sodium ions to migrate in the electrochemical process, resulting in slower reaction kinetics for SIBs and greater tendency to undergo large volume changes during cycling. Therefore, it is necessary to develop suitable anode materials for SIBs.
Among the cathode materials of sodium ion batteries, metal chalcogenide as a representative of conversion reaction materials has higher theoretical capacity and is expected to replace the current intercalation electrode materials. Metal selenides, which are a member of metal chalcogenides, are considered promising anode materials for SIBs. Selenides generally have a narrow band gap and have excellent electronic conductivity compared to metal sulfides. Meanwhile, the interaction of the metal-Se bond in the metal selenide is weaker than that of the metal-S bond, which is beneficial to the conversion reaction. However, the main problem faced by metal selenides is Na + The structure 'collapses' and even pulverizes caused by intercalation and deintercalation during charging and discharging, which directly affects the cycle and rate performance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides (NiCo) Se/(NiCo) Se 2 A @ C heterostructure composite material, a preparation method and application thereof, and provides (NiCo) Se/(NiCo) Se 2 The @ C heterostructure composite material and the preparation method and application thereof synthesize a novel bimetallic selenide negative electrode material by adopting hydrothermal and twice low-temperature heat treatment, compared with the traditional selenide, the heterostructure composite material with a continuous structure is obtained in polymer cracking and secondary selenizing environments, the structural stability and the rate capability of the material are favorably improved, and the heterostructure composite material can be finally displayed when being used in a sodium ion batteryHigher specific discharge capacity and good cycling stability.
The invention is realized by the following technical scheme:
(NiCo) Se/(NiCo) Se 2 A preparation method of the @ C heterostructure composite material comprises the following steps,
step 1, adding nickel salt and cobalt salt into a mixed solution of glycerol and isopropanol, stirring and mixing uniformly, then carrying out heating treatment, naturally cooling, centrifuging, washing and drying to obtain a precursor;
step 2, in inert atmosphere, annealing treatment is carried out after the precursor and selenium powder are evenly mixed to prepare (NiCo) Se 2 ；
Step 3, mixing the (NiCo) Se 2 Ultrasonically dispersing the mixture into an organic compound, stirring and mixing to obtain (NiCo) Se 2 @ organic composite material;
step 4, mixing the (NiCo) Se 2 The @ organic composite material and selenium powder are evenly mixed and then are annealed to prepare (NiCo) Se/(NiCo) Se 2 @ C heterostructure composite material.
Preferably, the nickel salt is Ni (NO) 3 ) 2 、NiCl 2 And NiSO 4 At least one of; the cobalt salt is Co (NO) 3 ) 2 、CoCl 2 And CoSO 4 At least one of (1).
Preferably, the molar ratio of the cobalt salt to the nickel salt is 1: (0.1-10).
Preferably, the volume ratio of the glycerol to the isopropanol is (0-0.3): 1.
preferably, the temperature of the heating treatment in the step 1 is 120-110 ℃, and the time of the heating treatment is 6-24 hours; the annealing temperature of the step 2 is 350-600 ℃, and the annealing time is 3-6 h; the annealing temperature in the step 4 is 600-100 ℃, and the annealing time is 2-6 h.
Preferably, the organic compound comprises one of PVP, PVDF, PVA, and dopamine hydrochloride; the PVP, PVDF and PVA and (NiCo) Se 2 Mixing by adopting a direct adding mode; the dopamine hydrochloride and (NiCo) Se 2 It is added into Tris buffer solution for mixing.
Preferably, the organic compound and (NiCo) Se in the step 3 2 The mass ratio is (1-4): 1.
preferably, the step 4 selenium powder and (NiCo) Se 2 The mass ratio of the @ organic composite material is (2-6): 1.
(NiCo) Se/(NiCo) Se 2 The @ C heterostructure composite material is prepared by the preparation method, and the (NiCo) Se/(NiCo) Se 2 The @ C heterostructure composite material is of a spherical structure.
(NiCo) Se/(NiCo) Se 2 The @ C heterostructure composite material is applied to sodium-ion batteries.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses (NiCo) Se/(NiCo) Se 2 The preparation method of the @ heterostructure bimetallic selenide cathode material comprises the steps of firstly obtaining a spherical precursor by a hydrothermal method, then obtaining a novel conventional bimetallic selenide material by two times of low-temperature heat treatment, and obtaining (NiCo) Se/(NiCo) Se with a heterostructure by organic matter wrapping and low-temperature selenization measures in the later stage 2 @ C composite material. The material maintains a spherical structure in the whole process, which is beneficial to improving the close packing state of the electrode and improving the volume energy density; the prepared (NiCo) Se/(NiCo) Se of the present invention is comparable to conventional selenides 2 The @ C heterostructure composite material is prepared by obtaining a heterostructure composite material with a continuous structure in a polymer cracking and secondary selenization environment, is favorable for improving the structural stability and rate capability of the material, and can show higher discharge specific capacity and good cycling stability when finally used in a sodium ion battery.
Further, the spherical precursor provided by the invention has a relatively stable structure in the processes of post-heat treatment and the like, and the solution environment has obvious influence on the structure and stability of the precursor, so that the volume ratio of glycerol to isopropanol is set to be (0-0.3): 1, the method has simple preparation process and good controllability and consistency.
Furthermore, the heterostructure material obtained by the inventionThe material is different from the traditional mutual composition of different component substances, but adopts polymer and low-temperature secondary selenization technology to directly compound the traditional (NiCo) Se 2 In-situ derivatization to (NiCo) Se/(NiCo) Se 2 @ C, not only promoted the continuity of material inner structure, can also carry out carbon-coated to the material through polymer pyrolysis, promotion material conductivity that can kill two birds with one stone suppresses the volume expansion among the charge-discharge process.
The invention also discloses the (NiCo) Se/(NiCo) Se of the prepared heterostructure 2 The application of the @ C composite material in the sodium ion battery can effectively improve the reaction kinetics and stability of the battery when the obtained material is used as a negative electrode, and the highest current density of the material can reach 30A g -1 And all the materials are kept stable in the 200-time circulation process, the characteristics of high specific capacity and low circulation attenuation rate are presented, and the method has good implementation and development prospects in sodium-ion batteries.
Drawings
FIG. 1 is an SEM image of a precursor prepared in example 1;
FIG. 2 is (NiCo) Se prepared in example 1 2 SEM picture of (1);
FIG. 3 is (NiCo) Se/(NiCo) Se prepared in example 1 2 SEM images of @ C heterostructure composites;
FIG. 4 is (NiCo) Se/(NiCo) Se prepared in example 1 2 A @ C heterostructure composite material multiplying power test chart;
fig. 5 is a graph showing a cycle comparison of the samples prepared in example 1 and comparative example 1.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
(NiCo) Se/(NiCo) Se 2 The preparation method of the @ C heterostructure composite material comprises the steps of adding nickel salt and cobalt salt into a mixed solution of glycerol and isopropanol, uniformly stirring, then carrying out heating treatment, naturally cooling, centrifuging, washing and drying to obtain a precursor; under inert atmosphere, the precursor and selenium powder are evenly mixed and then are annealed to prepare (NiCo) Se 2 . Adding (NiCo) Se 2 Ultrasonically dispersing into PVP, PVDF, PVA or dopamine hydrochloride solution, and stirring to obtain the organic (organic) coated composite ((NiCo) Se) 2 @ organic); mixing (NiCo) Se 2 The @ organic composite material and selenium powder are evenly mixed and then are annealed to prepare (NiCo) Se/(NiCo) Se 2 @ C heterostructure composite material. Wherein, polyvinylpyrrolidone is PVP for short; polyvinylidene fluoride (PVDF) is a highly non-reactive thermoplastic fluoropolymer, and PVA is a polyvinyl alcohol material;
specifically, the addition ratio of the cobalt salt to the nickel salt is 1: (0.1-10).
Specifically, the volume ratio of glycerol to isopropanol is (0-0.3): 1.
specifically, the heating treatment temperature is 120-110 ℃, and the heating treatment is naturally cooled after the duration time is 6-24 hours.
Specifically, the annealing temperature is 350-600 ℃, and the annealing time is 3-6 h.
Specifically, the mass ratio of the precursor to the selenium powder is (0.5-1): 1.
specifically, in the organic matter for wrapping, except that Tris solution is required to be added for controlling dopamine polymerization when dopamine hydrochloride is wrapped, other organic matters (PVP, PVDF and PVA) are directly added.
In particular, the organic substance and (NiCo) Se are added 2 The mass ratio is (1-4): 1.
in particular, selenium powder and (NiCo) Se 2 The mass ratio of the @ organic composite material is (2-6): 1.
specifically, the annealing temperature is 600-100 ℃, and the annealing time is 2-6 h.
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The following detailed description is illustrative of the embodiments and is intended to provide further details of the invention. Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the invention.
Example 1
(1) 0.116g of Ni (NO) was weighed out 3 ) 2 ·6H 2 O、0.051g Co(NO 3 ) 2 ·6H 2 O was dissolved in a mixed solution of 7.5mL of glycerin and 52.5mL of isopropyl alcohol. The resulting solution was then transferred to a 100mL Teflon lined reactor and heated at 110 ℃ for 6 h. Centrifuging, washing and vacuum drying to obtain the precursor. Secondly, the precursor and Se powder are mixed in a mass ratio of 1:2 and thoroughly ground. Annealing for 6 hours at 350 ℃ in inert atmosphere to obtain (NiCo) Se 2 。
(2) Ultrasonically dispersing 50mg of the synthesized selenide into 50ml of Tris buffer solution (10mM, pH 1-9), adding dopamine (50mg) under vigorous stirring, and continuously stirring for 6h to obtain (NiCo) Se 2 @ PDA composite material.
(3) 50mg of (NiCo) Se 2 The @ PDA composite and Se powder were mixed in a mass ratio of 1:2 and thoroughly ground. Annealing for 2h at 600 ℃ in an inert atmosphere to obtain (NiCo) Se/(NiCo) Se 2 @ C heterostructure composite.
SEM image of the prepared precursor as shown in fig. 1; FIG. 2 is (NiCo) Se prepared 2 SEM picture of (1);
FIG. 3 shows the preparation of (NiCo) Se/(NiCo) Se 2 SEM images of @ C heterostructure composites; the material maintains a spherical structure in the whole preparation process, so that the close packing state of the electrode is favorably improved, and the volume energy density is improved;
example 2
(1) Weighing 0.051g Ni (NO) 3 ) 2 ·6H 2 O、0.051g Co(NO 3 ) 2 ·6H 2 O was dissolved in a mixed solution of 7.5mL of glycerin and 52.5mL of isopropyl alcohol. The resulting solution was then transferred to a 100mL Teflon lined reactor and heated at 110 ℃ for 6 h. Centrifuging, washing and vacuum drying to obtain the precursor. Secondly, the precursor and Se powder are mixed in a mass ratio of 1:2 and thoroughly ground. Annealing for 6 hours at 350 ℃ in inert atmosphere to obtain (NiCo) Se 2 。
(2) Ultrasonically dispersing 50mg of the synthesized selenide into 50ml of Tris buffer solution (10mM, pH 1-9), adding dopamine (50mg) under vigorous stirring, and continuously stirring for 6h to obtain (NiCo) Se 2 @ PDA composite material.
(3) 50mg of (NiCo) Se 2 The @ PDA composite and Se powder were mixed in a mass ratio of 1:2 and thoroughly ground. Annealing for 2h at 600 ℃ in an inert atmosphere to obtain (NiCo) Se/(NiCo) Se 2 @ C heterostructure composite material.
Example 3
(1) Weighing 0.051g Ni (NO) 3 ) 2 ·6H 2 O、0.51g Co(NO 3 ) 2 ·6H 2 O was dissolved in a mixed solution of 1mL of glycerin and 40mL of isopropyl alcohol. The resulting solution was then transferred to a 100mL Teflon lined reactor and heated at 110 ℃ for 24 h. Centrifuging, washing and vacuum drying to obtain the precursor. Secondly, the precursor and the Se powder are mixed in a mass ratio of 1:2 and thoroughly ground. Annealing for 6 hours at 350 ℃ in inert atmosphere to obtain (NiCo) Se 2 。
(2) Ultrasonically dispersing 50mg of synthesized selenide into a PVDF solution, and continuously stirring for 6 hours to obtain (NiCo) Se 2 @ PVDF composite.
(3) 50mg of (NiCo) Se 2 @ PVDF composite and Se powder were mixed in a mass ratio of 1:2 and thoroughly ground. Annealing for 2h at 600 ℃ in an inert atmosphere to obtain (NiCo) Se/(NiCo) Se 2 @ C heterostructure composite material.
Example 4
(1) 0.116g of Ni (NO) was weighed out 3 ) 2 ·6H 2 O、0.051g Co(NO 3 ) 2 ·6H 2 O was dissolved in a mixed solution of 7.5mL of glycerin and 52.5mL of isopropyl alcohol. The resulting solution was then transferred to a 100mL Teflon lined reactor and heated at 110 ℃ for 6 h. Centrifuging, washing and vacuum drying to obtain the precursor. Secondly, the precursor and the Se powder are mixed in a mass ratio of 1:2 and thoroughly ground. Annealing for 6h at 350 ℃ in inert atmosphere to obtain (NiCo) Se 2 。
(2) Ultrasonically dispersing 50mg of synthesized selenide into PVP solution, and continuously stirring for 12h to obtain (NiCo))Se 2 @ PVP composite.
(3) 50mg of (NiCo) Se 2 @ PVP composite and Se powder were mixed in a mass ratio of 1:2 and thoroughly ground. Annealing for 2h at 600 ℃ in an inert atmosphere to obtain (NiCo) Se/(NiCo) Se 2 @ C heterostructure composite material.
Example 5
(1) 0.116g of Ni (NO) was weighed out 3 ) 2 ·6H 2 O、0.051g Co(NO 3 ) 2 ·6H 2 O was dissolved in a mixed solution of 7.5mL of glycerin and 52.5mL of isopropyl alcohol. The resulting solution was then transferred to a 100mL Teflon lined reactor and heated at 110 ℃ for 6 h. Centrifuging, washing and vacuum drying to obtain the precursor. Secondly, the precursor and the Se powder are mixed in a mass ratio of 1:2 and thoroughly ground. Annealing for 6 hours at 350 ℃ in inert atmosphere to obtain (NiCo) Se 2 。
(2) Ultrasonically dispersing 50mg of the synthesized selenide into 50ml of Tris buffer solution (10mM, pH 1-9), adding dopamine (50mg) under vigorous stirring, and continuously stirring for 6h to obtain (NiCo) Se 2 @ PDA composite material.
(3) 50mg of (NiCo) Se 2 The @ PDA composite and Se powder were mixed in a mass ratio of 1:6 and thoroughly ground. Annealing for 2h at 600 ℃ in an inert atmosphere to obtain (NiCo) Se/(NiCo) Se 2 @ C heterostructure composite material.
The bimetallic selenides prepared in the above examples were selected and tested for electrochemical performance by assembling button half cells in an argon-filled glove box. And the negative electrode takes N-methyl pyrrolidone (NMP) as a solvent, and the mass ratio of an active substance, conductive carbon black and polyvinylidene fluoride (PVDF) is 7: 2: 1, uniformly mixing, coating on a copper foil, putting into a vacuum drying oven, vacuum-drying for 12 hours at 110 ℃, and naturally cooling to room temperature. The half-cell assembly was carried out by cutting into 12mm wafers by a cutter, weighing, and then putting into a glove box filled with argon gas. In the assembly of the half-cell, a metal sodium sheet, glass fibers (Whatman GF/F) and 1.0M NaCF 3 SO 3 Taking DEGDME as electrolyte as counter electrode, diaphragm and electrolyte, standing at room temperature for 12h after assembly, and performing electrochemical performance measurement after the electrolyte is completely soakedAnd (6) testing.
Comparative example 1
(1) 0.116g of Ni (NO) was weighed out 3 ) 2 ·6H 2 O、0.051g Co(NO 3 ) 2 ·6H 2 O was dissolved in a mixed solution of 7.5mL of glycerin and 52.5mL of isopropyl alcohol. The resulting solution was then transferred to a 100mL Teflon lined reactor and heated at 110 ℃ for 6 h. Centrifuging, washing and vacuum drying to obtain the precursor. Secondly, the precursor and the Se powder are mixed in a mass ratio of 1:2 and thoroughly ground. Annealing for 6 hours at 350 ℃ in inert atmosphere to obtain (NiCo) Se 2 。
(2) Ultrasonically dispersing 50mg of the synthesized selenide into 50ml of Tris buffer solution (10mM, pH 1-9), adding dopamine (50mg) under vigorous stirring, and continuously stirring for 6h to obtain (NiCo) Se 2 @ PDA composite material.
(3) 50mg of (NiCo) Se 2 And (2) annealing the @ PDA composite material for 2h at 600 ℃ in an inert atmosphere without adding selenium powder to obtain the (NiCo) Se @ C composite material. .
The bimetallic selenides prepared in the above examples were selected and tested for electrochemical performance by assembling button half cells in an argon-filled glove box. The negative electrode takes N-methylpyrrolidone (NMP) as a solvent, and an active substance, conductive carbon black and polyvinylidene fluoride (PVDF) are mixed according to a mass ratio of 7: 2: 1, uniformly mixing, coating on a copper foil, putting into a vacuum drying oven, vacuum-drying for 12 hours at 110 ℃, and naturally cooling to room temperature. 12mm round pieces were cut out by a cutter, weighed, and then put into a glove box filled with argon gas to perform half-cell assembly. In the assembly of the half-cell, a metal sodium sheet, glass fibers (Whatman GF/F) and 1.0M NaCF 3 SO 3 And taking DEGDME as an electrolyte as a counter electrode, a diaphragm and the electrolyte, standing for 12 hours at room temperature after the assembly is finished, and carrying out electrochemical test after the electrolyte is completely soaked.
Referring to FIG. 4, to obtain (NiCo) Se/(NiCo) Se 2 The multiplying power performance diagram of the @ C heterostructure composite material is that the test voltage interval is 0.01-3V, and the current density is from 1A g -1 Increased to 30A g -1 When the current density is 1A g -1 The discharge capacity was 540.9mA h g -1 When the current density was increased to 30A g -1 While the electrode can still provide 324.9mA h g -1 Capacity. In addition, when the current density was restored to 1A g -1 Reversible capacity can be restored to 523.1mA h g -1 And exhibits excellent reversibility.
Referring to FIG. 5, the cycle of the duplex selenides prepared in example 1 and comparative example 1 is compared, and comparative example 1 is shown at 5A g -1 The reversible specific capacity after 110 cycles of circulation under the current density is only 222.7mA h g -1 And has a lower capacity. Example 1 at 5A g -1 The reversible specific capacity after 110 cycles under the current density is still kept at 425.1mA h g -1 The capacity retention rate is 12.4%, and the better cycle stability is shown.
In summary, the invention provides (NiCo) Se/(NiCo) Se 2 The @ C heterostructure composite material and the preparation method and the application thereof. Compared with the prior art, the product of the invention has low cost, environmental protection, stable material structure and good reproducibility. The material was used in sodium ion batteries at 5A g -1 The reversible specific capacity after 110 cycles of circulation under the current density is still kept at 425.1mA h g -1 The capacity retention rate was 12.4%. When the current density was increased to 30A g -1 While the electrode can still provide 324.9mA h g -1 The capacity shows excellent discharge capacity, rate performance and long-term cycling stability, and has good application prospect in developing a cheap high-performance sodium ion battery system.
Claims (10)
1. (NiCo) Se/(NiCo) Se 2 A preparation method of the @ C heterostructure composite material is characterized by comprising the following steps,
step 1, adding nickel salt and cobalt salt into a mixed solution of glycerol and isopropanol, stirring and mixing uniformly, then carrying out heating treatment, naturally cooling, centrifuging, washing and drying to obtain a precursor;
step 2, under inert atmosphere, uniformly mixing the precursor and selenium powder, and then carrying out annealing treatment to obtain (NiCo) Se 2 ；
Step 3, mixing the (NiCo) Se 2 Ultrasonically dispersing into an organic compound, stirring and mixing to obtain (NiCo) Se 2 @ organic composite material;
step 4, mixing the (NiCo) Se 2 The @ organic composite material and selenium powder are evenly mixed and then are annealed to prepare (NiCo) Se/(NiCo) Se 2 @ C heterostructure composite material.
2. A (NiCo) Se/(NiCo) Se according to claim 1 2 The preparation method of the @ C heterostructure composite material is characterized in that Ni (NO) is adopted as the nickel salt 3 ) 2 、NiCl 2 And NiSO 4 At least one of; the cobalt salt is Co (NO) 3 ) 2 、CoCl 2 And CoSO 4 At least one of (1).
3. A (NiCo) Se/(NiCo) Se according to claim 1 2 The preparation method of the @ C heterostructure composite material is characterized in that the molar ratio of the cobalt salt to the nickel salt is 1: (0.1-10).
4. A (NiCo) Se/(NiCo) Se according to claim 1 2 The preparation method of the @ C heterostructure composite material is characterized in that the volume ratio of glycerol to isopropanol is (0-0.3): 1.
5. a (NiCo) Se/(NiCo) Se according to claim 1 2 The preparation method of the @ C heterostructure composite material is characterized in that the heating treatment temperature in the step 1 is 120-180 ℃, and the heating treatment time is 6-24 hours; the annealing temperature of the step 2 is 350-600 ℃, and the annealing time is 3-6 h; the annealing temperature in the step 4 is 600-800 ℃, and the annealing time is 2-6 h.
6. A (NiCo) Se/(NiCo) Se according to claim 1 2 The preparation method of the @ C heterostructure composite material is characterized in that the organic compound comprises one of PVP, PVDF, PVA and dopamine hydrochloride; the PVP, PVDF and PVA and (NiCo) Se 2 By usingMixing by direct adding; the dopamine hydrochloride and (NiCo) Se 2 It is added into Tris buffer solution for mixing.
7. The method for preparing a (NiCo) Se/(NiCo) Se2@ C heterostructure composite material according to claim 1, wherein the organic compound and the (NiCo) Se in the step 3 2 The mass ratio is (1-4): 1.
8. a (NiCo) Se/(NiCo) Se according to claim 1 2 The preparation method of the @ C heterostructure composite material is characterized in that the selenium powder and (NiCo) Se are mixed in the step 4 2 The mass ratio of the @ organic composite material is (2-6): 1.
9. (NiCo) Se/(NiCo) Se 2 @ C heterostructure composite material, characterized in that it is obtained on the basis of the preparation process according to any one of claims 1 to 8, the (NiCo) Se/(NiCo) Se 2 The @ C heterostructure composite material is of a spherical structure.
10. A (NiCo) Se/(NiCo) Se as claimed in claim 9 2 @ C heterostructure composite, or (NiCo) Se/(NiCo) Se according to any of claims 1 to 8 2 (NiCo) Se/(NiCo) Se prepared by preparation method of @ C heterostructure composite material 2 The @ C heterostructure composite material is applied to a sodium ion battery.
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