CN107394177B - Nickel bicarbonate/graphene composite material for sodium-ion battery cathode and preparation method and application thereof - Google Patents
Nickel bicarbonate/graphene composite material for sodium-ion battery cathode and preparation method and application thereof Download PDFInfo
- Publication number
- CN107394177B CN107394177B CN201710652052.0A CN201710652052A CN107394177B CN 107394177 B CN107394177 B CN 107394177B CN 201710652052 A CN201710652052 A CN 201710652052A CN 107394177 B CN107394177 B CN 107394177B
- Authority
- CN
- China
- Prior art keywords
- nickel
- composite material
- sodium
- bicarbonate
- ion battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- IYFXESRMJKRSNZ-UHFFFAOYSA-L hydrogen carbonate;nickel(2+) Chemical compound [Ni+2].OC([O-])=O.OC([O-])=O IYFXESRMJKRSNZ-UHFFFAOYSA-L 0.000 title claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 40
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 26
- 150000002815 nickel Chemical class 0.000 claims abstract description 24
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000007773 negative electrode material Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 7
- 239000004202 carbamide Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000004277 Ferrous carbonate Substances 0.000 abstract 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 abstract 1
- 229960004652 ferrous carbonate Drugs 0.000 abstract 1
- 235000019268 ferrous carbonate Nutrition 0.000 abstract 1
- 229910000015 iron(II) carbonate Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- -1 graphene modified nickel bicarbonate Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910020293 Na2Ti3O7 Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a nickel bicarbonate/graphene composite material for a sodium-ion battery cathode, and a preparation method and application thereof. The invention adopts a hydrothermal method, takes graphene oxide, divalent nickel salt, a reducing agent and water-soluble carbonate or urea as raw materials, and prepares the ferrous carbonate/graphene composite material. The composite material has uniform size, is applied to a sodium ion cathode, has good electrochemical performance, and has excellent rate performance and cycle stability. In addition, the preparation method of the invention has strong operability and good reproducibility, and the obtained product has stable quality.
Description
Technical Field
The invention relates to a nickel bicarbonate/graphene composite material for a sodium ion battery cathode, and a preparation method and application thereof, and belongs to the technical field of electrochemistry.
Background
Compared with the lithium ion battery, the sodium ion battery has the advantages of abundant sodium resource reserves and low raw material price, and has a wide application prospect in the field of large-scale energy storage. The negative electrode material of the sodium ion battery, which is one of important components of the battery, has important influence on the performance of the battery. At present, the sodium storage negative electrode material of the intercalation mechanism is concerned more because of the higher cycle stability, and mainly comprises hard carbon and Na2Ti3O7And Li4Ti5O12And the like. Among these sodium-storing negative electrode materials, Na2Ti3O7And Li4Ti5O12The specific capacity of (A) is usually less than 200mAh g-1And the requirement of a high-capacity energy storage battery is difficult to meet. The sodium storage capacity of the hard carbon can reach 300mAh g-1But its rate capability is poor and most of its capacity is below 0.1V (vs. Na/Na) at discharge voltage+) The potential is very close to the precipitation potential of metallic sodium, which can cause the formation of sodium dendrites on the surface of the electrode and bring about a serious safety hazard. Therefore, the search for a novel sodium-electricity negative electrode material with high specific capacity, better rate performance, better cycling stability and high safety is of great significance.
At present, in the prior art, it has been reported that the specific capacity, rate capability and cycle performance of a sodium ion battery are improved by preparing a graphene composite material and applying the graphene composite material to a sodium ion battery cathode material. For example, chinese patent document CN105789592A discloses a three-dimensional graphene composite electrode, which uses three-dimensional porous nickel foam as a substrate, and graphene is directly grown on the substrate, and flower-like Ni is directly grown on the graphene3S2. The three-dimensional graphene-based composite electrode prepared by the method does not contain any conductive agent and binder, and is prepared by firstly carrying out a chemical vapor deposition method and then carrying out hydrothermal treatmentThe preparation method is adopted to obtain; but the steps are more complicated, and the prepared material has poor specific capacity when being used for the sodium ion battery.
Nickel hydrogen carbonate is a negative electrode material of a conversion mechanism lithium ion battery which is researched more at present, and has higher theoretical capacity (300 mAh g) of lithium storage-1Based on conversion reactions) Proper discharge voltage (1.0V), easy preparation, less environmental pollution and other advantages. However, there is no report on the application of nickel bicarbonate to the negative electrode material of sodium ion battery. However, nickel bicarbonate as a negative electrode material of a sodium ion battery has the defects of unstable structure and low conductivity caused by large volume change in the circulation process.
Accordingly, the present invention has been made to solve the above problems.
Disclosure of Invention
In order to make up for the defects of the conventional sodium-ion battery cathode material, the invention provides a nickel bicarbonate/graphene composite material for a sodium-ion battery cathode and a preparation method thereof. The preparation method of the composite material is simple, the operability is strong, the reproducibility is good, and the obtained product has stable quality.
The invention also provides an application of the nickel bicarbonate/graphene composite material, and the composite material applied to the negative electrode material of the sodium-ion battery can effectively improve the charge-discharge rate and the cycle performance.
The technical scheme of the invention is as follows:
a nickel bicarbonate/graphene composite material for a sodium ion battery cathode is a composite powder material of nickel bicarbonate and graphene, and the mass content of the nickel bicarbonate in the composite powder material is 60-95%.
According to the invention, the composite powder material preferably contains 80-95% of nickel bicarbonate by mass.
According to the invention, the preferable micro-morphology of the nickel bicarbonate/graphene composite material is as follows: the nickel bicarbonate nanoparticles are uniformly loaded on the graphene sheet; the particle size of the nickel bicarbonate nano particles is 10 nm-5 mu m; preferably, the particle size of the nickel bicarbonate nanoparticles is 10-500 nm.
The preparation method of the nickel bicarbonate/graphene composite material for the negative electrode of the sodium-ion battery comprises the following steps:
dispersing graphene oxide in deionized water, adding a divalent nickel salt, a reducing agent and water-soluble carbonate or urea, and uniformly mixing to obtain a reaction solution; carrying out hydrothermal reaction for 1-48 hours at the temperature of 70-200 ℃, and washing and drying to obtain the nickel bicarbonate/graphene composite material.
According to the present invention, the graphene oxide may be commercially available or prepared according to the prior art.
According to the present invention, it is preferable that the ratio of the mass of the graphene oxide to the amount of the divalent nickel salt substance in the reaction solution is 1: 0.01-0.5 g/mol; preferably, the ratio of the mass of the graphene oxide to the amount of the divalent nickel salt substance is 1: 0.02-0.2 g/mol.
According to the invention, the molar concentration of the divalent nickel salt in the reaction liquid is preferably 0.01-0.25 mol/L; preferably, the divalent nickel salt has a molar concentration of 0.025 to 0.125 mol/L.
According to the present invention, it is preferable that the amount ratio of the reducing agent, the water-soluble carbonate or urea and the divalent nickel salt in the reaction liquid is 0.5 to 1.5: 5-25: 1-5; preferably, the ratio of the amounts of the reducing agent, water-soluble carbonate or urea and divalent nickel salt is 0.5-1.5: 5-10: 1-3.
According to the present invention, preferably, the divalent nickel salt is one of nickel nitrate, nickel chloride, nickel sulfate or nickel acetate.
Preferably, according to the present invention, the reducing agent is one of citric acid, glucose or ascorbic acid.
Preferably according to the invention, the water-soluble carbonate is ammonium carbonate or sodium carbonate; preferably, the water-soluble carbonate is ammonium carbonate.
According to the invention, the water-soluble carbonate is preferably used in a molar concentration of 0.05 to 1.25mol L-1The water-soluble carbonate aqueous solution of (1).
Preferably, the preparation method of the reaction solution comprises the following steps: dispersing graphene oxide in deionized water, adding a divalent nickel salt and a reducing agent, dissolving and mixing uniformly, quickly adding a carbonate aqueous solution, and mixing uniformly to obtain a reaction solution.
According to the invention, the hydrothermal reaction temperature is preferably 160-180 ℃, and the reaction time is preferably 2-6 hours.
Preferably according to the invention, the drying conditions are: drying at 60-90 deg.C for 6-24 hr in air or vacuum.
The application of the nickel bicarbonate/graphene composite material for the negative electrode of the sodium-ion battery is used as a negative electrode material of the sodium-ion battery to be applied to the sodium-ion battery; the sodium ion battery comprises a negative electrode made of a nickel bicarbonate/graphene composite material, a positive electrode capable of releasing sodium ions and an electrolyte between the negative electrode and the positive electrode.
The mass percentage of nickel bicarbonate in the nickel bicarbonate/graphene composite material can be regulated and controlled by controlling the mass molar ratio of graphene oxide to divalent nickel salt.
The invention also provides a preparation method of the nickel bicarbonate, which comprises the following steps:
dissolving a divalent nickel salt, a reducing agent and water-soluble carbonate or urea in deionized water, and uniformly mixing to obtain a reaction solution; carrying out hydrothermal reaction for 1-48 hours at the temperature of 70-200 ℃, and washing and drying to obtain nickel bicarbonate;
the molar concentration of the divalent nickel salt in the reaction liquid is 0.01-0.25 mol/L; preferably, the divalent nickel salt has a molar concentration of 0.025 to 0.125 mol/L.
The mass ratio of the reducing agent, the water-soluble carbonate or urea and the divalent nickel salt is 0.5-1.5: 5-25: 1-5; preferably, the ratio of the amounts of the reducing agent, water-soluble carbonate or urea and divalent nickel salt is 0.5-1.5: 5-10: 1-3.
The divalent nickel salt is one of nickel nitrate, nickel chloride, nickel sulfate or nickel acetate;
the water-soluble carbonate is ammonium carbonate or sodium carbonate; preferably, the water-soluble carbonate is ammonium carbonate;
the water-soluble carbonate is used at a molar concentration of 0.05-1.25mol L-1An aqueous solution of a water-soluble carbonate salt of (4).
Preferably, the preparation method of the reaction solution comprises the following steps: dissolving a divalent nickel salt and a reducing agent in deionized water, quickly adding a carbonate aqueous solution, and uniformly mixing to obtain a reaction solution.
The nickel bicarbonate is applied to the sodium ion battery as a negative electrode material of the sodium ion battery.
The invention has the following technical characteristics and beneficial effects:
(1) the reducing agent is added in the preparation process, and is used for reducing graphene oxide into graphene in the reaction process and inhibiting oxidation of divalent nickel. The carbonate aqueous solution is quickly poured into the preparation method, mainly because carbonate and metal ions can quickly form a carbonate precursor, the particle size of the precursor can be reduced by quickly pouring the carbonate and the metal ions into the preparation method, and meanwhile, a uniform carbonate precursor and graphene oxide composite material is obtained, and finally, the nickel bicarbonate/graphene composite material obtained through hydrothermal reaction has the characteristic of uniform distribution of components. The micro-morphology of the composite material prepared by the invention is that nickel bicarbonate nano-particles with the particle size of 50-150nm are uniformly loaded on graphene sheets.
(2) The nickel bicarbonate can generate reversible electrochemical conversion reaction with sodium ions Theoretical capacity of 300mAh g-1) The graphene modified nickel bicarbonate can inhibit the volume effect and improve the conductivity of the material, thereby further improving the specific capacity, the multiplying power and the cycle performance of the material.
(3) The nickel bicarbonate/graphene composite material is synthesized by a hydrothermal method in one step, the preparation method is simple, the cost is low, the method has strong operability and good reproducibility, and the obtained product has stable quality.
(4) When the nickel bicarbonate/graphene composite material prepared by the invention is applied to a sodium ion battery cathode material, the surprising discovery that the nickel bicarbonate/graphene composite material shows excellent specific capacity, cycle performance and rate capability, and simultaneously shows good rate and cycle performance under the condition of large current charging and discharging is surprisingly found, and the specific capacity of the nickel bicarbonate/graphene composite material reaches 107mAh/g under the current density of 2A/g; after 50 cycles under 100mA/g, the specific capacity of 266mAh/g can be kept; the method provides a new choice for the application of the sodium-ion battery cathode material, lays a foundation for the possible high-current charge and discharge application of the sodium-ion battery cathode material, and can further provide application products for high-current charge and discharge on electric vehicles.
Drawings
Fig. 1 is an XRD spectrum of the nickel bicarbonate/graphene composite material prepared in example 1 of the present invention.
Fig. 2 is a scanning electron micrograph of the nickel bicarbonate/graphene composite material prepared in example 1 of the present invention.
Fig. 3 is a graph comparing the electrochemical performance rate performance of nickel bicarbonate and nickel bicarbonate/graphene composite material in application example 1 of the present invention.
Fig. 4 is a graph comparing electrochemical cycle performance of nickel bicarbonate and nickel bicarbonate/graphene composite material in application example 1 of the present invention.
Detailed Description
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.
Graphene oxide is commercially available from Shandonghai chemical group in the examples.
Example 1
A nickel bicarbonate/graphene composite material for a sodium ion battery cathode is a composite powder material of nickel bicarbonate and graphene, wherein the mass content of nickel bicarbonate in the composite powder material is 92%.
The preparation method of the nickel bicarbonate/graphene composite material for the negative electrode of the sodium-ion battery comprises the following steps:
taking 6mg of graphene oxide, ultrasonically dispersing in 35mL of deionized water, then adding 1mmol of nickel chloride and 0.2g of ascorbic acid, stirring for 15 minutes at room temperature, and finally quickly adding 5mL of ammonium carbonate aqueous solution (1mol L)-1) Mixing evenly, transferring into a 50mL polytetrafluoroethylene reaction kettle, and reacting for 5 hours at the temperature of 160 ℃. And washing the obtained product, and drying the product in the air at the temperature of 80 ℃ for 6 hours to obtain the nickel bicarbonate/graphene composite material.
The XRD spectrum of the nickel bicarbonate/graphene composite material prepared in this example is shown in fig. 1, and it can be seen from fig. 1 that the prepared composite material is a composite of nickel bicarbonate and graphene.
A scanning electron micrograph of the nickel bicarbonate/graphene composite material prepared in this example is shown in fig. 2, and it can be seen from fig. 2 that nickel bicarbonate nanoparticles having a micro-morphology of about 60nm are loaded on graphene sheets.
Example 2
A preparation method of a nickel bicarbonate/graphene composite material for a sodium-ion battery cathode comprises the following steps:
taking 6mg of graphene oxide, ultrasonically dispersing in 35mL of deionized water, then adding 2mmol of nickel chloride and 0.2g of ascorbic acid, stirring for 15 minutes at room temperature, and finally quickly adding 5mL of ammonium carbonate aqueous solution (1mol L)-1) Mixing evenly, transferring into a 50mL polytetrafluoroethylene reaction kettle, and reacting for 3 hours at the temperature of 180 ℃. And washing the obtained product, and drying the product in the air at the temperature of 80 ℃ for 6 hours to obtain the nickel bicarbonate/graphene composite material.
Example 3
A preparation method of a nickel bicarbonate/graphene composite material for a sodium-ion battery cathode comprises the following steps:
taking 6mg of graphene oxide, ultrasonically dispersing in 35mL of deionized water, then adding 3mmol of nickel acetate and 0.2g of glucose, stirring for 15 minutes at room temperature, and finally quickly adding 5mL of ammonium carbonate aqueous solution (1mol L)-1) Mixing ofMixing evenly, transferring the mixture into a 50mL polytetrafluoroethylene reaction kettle, and reacting for 5 hours at the temperature of 160 ℃. And washing the obtained product, and drying the product in the air at the temperature of 80 ℃ for 6 hours to obtain the nickel bicarbonate/graphene composite material.
Example 4
A preparation method of nickel bicarbonate comprises the following steps:
1mmol of nickel chloride and 0.2g of ascorbic acid were added to 35mL of deionized water, and 5mL of an aqueous ammonium carbonate solution (1mol L) were rapidly added-1) Then, the mixture was stirred at room temperature for 15 minutes, and then transferred to a 50mL polytetrafluoroethylene reaction vessel to be reacted at 160 ℃ for 5 hours. And washing and drying the obtained product in air at 80 ℃ for 6 hours to obtain the nickel bicarbonate material.
Application example 1
The materials prepared in example 1 and example 4 were applied as active materials to negative electrode materials of sodium ion batteries, and electrochemical properties thereof were tested. The preparation method of the electrode comprises the following steps: mixing a conductive agent: adhesive: the active material (material prepared in example 1 and example 5) was mixed at a ratio of 10: 10: 80 to prepare slurry (acetylene black is adopted as a conductive agent, CMC is adopted as a binder), and the slurry is uniformly coated on the copper foil current collector by controlling a certain thickness. Cutting electrode plates with proper sizes, baking at 80 ℃ for 12 hours in vacuum, forming a button cell in a glove box, taking a sodium plate as a counter electrode, and adding 1mol/L NaClO4EC/DMC (volume ratio 1:1) is electrolyte, and the diaphragm is glass fiber filter paper, so as to form the button cell (CR 2032). The working interval of the battery is 0.01V-3.0V.
Fig. 3 is a graph showing the rate performance of the nickel bicarbonate prepared in example 4 and the nickel bicarbonate/graphene composite material prepared in example 1, and as can be seen from fig. 3, under a current density of 2A/g, the specific capacity of the nickel bicarbonate/graphene composite material reaches 107mAh/g, the specific capacity of the nickel bicarbonate is 64mAh/g, which is greatly improved compared with that of a single nickel bicarbonate, so that the specific capacity and the rate performance of the nickel bicarbonate material are greatly improved by introducing the graphene.
Fig. 4 is a comparison graph of cycle performance of the nickel bicarbonate prepared in example 4 and the nickel bicarbonate/graphene composite material prepared in example 1 at 100mA/g, the nickel bicarbonate/graphene composite material can maintain a specific capacity of 266mAh/g after 50 cycles, the nickel bicarbonate can maintain a specific capacity of 147mAh/g, and the nickel bicarbonate/graphene composite material shows significantly enhanced electrochemical stability compared with a single nickel bicarbonate material. Most of the capacity of the invention is realized at about 1.0V of discharge voltage.
Claims (3)
1. The application of the nickel bicarbonate/graphene composite material for the negative electrode of the sodium-ion battery is used as the negative electrode material of the sodium-ion battery to be applied to the sodium-ion battery; the sodium ion battery comprises a cathode made of a nickel bicarbonate/graphene composite material, an anode capable of releasing sodium ions and an electrolyte between the cathode and the anode;
the composite material is a composite powder material of nickel bicarbonate and graphene, and the mass content of the nickel bicarbonate in the composite powder material is 80-95%; the micro-morphology of the nickel bicarbonate/graphene composite material is as follows: the nickel bicarbonate nanoparticles are uniformly loaded on the graphene sheet; the particle size of the nickel bicarbonate nano particles is 10-500 nm;
the preparation method comprises the following steps:
dispersing graphene oxide in deionized water, adding a divalent nickel salt and a reducing agent, dissolving and mixing uniformly, quickly adding a carbonate aqueous solution, and mixing uniformly to obtain a reaction solution; carrying out hydrothermal reaction for 2-6 hours at the temperature of 160-180 ℃, and washing and drying to obtain a nickel bicarbonate/graphene composite material;
the divalent nickel salt is one of nickel nitrate, nickel chloride, nickel sulfate or nickel acetate; the reducing agent is one of citric acid, glucose or ascorbic acid; the ratio of the mass of the graphene oxide to the amount of the divalent nickel salt in the reaction solution is 1: 0.02-0.2 g/mol; the molar concentration of the divalent nickel salt in the reaction liquid is 0.01-0.25 mol/L; the mass ratio of the reducing agent, the carbonate and the divalent nickel salt in the reaction solution is 0.5-1.5: 5-25: 1-5.
2. The use of the nickel bicarbonate/graphene composite material for the negative electrode of the sodium-ion battery according to claim 1, wherein the ratio of the amounts of the reducing agent, the carbonate and the divalent nickel salt is 0.5-1.5: 5-10: 1-3.
3. The use of the nickel bicarbonate/graphene composite material for the negative electrode of the sodium-ion battery according to claim 1, wherein the carbonate is ammonium carbonate or sodium carbonate; the molar concentration of the carbonate aqueous solution is 0.05-1.25mol L-1。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710652052.0A CN107394177B (en) | 2017-08-02 | 2017-08-02 | Nickel bicarbonate/graphene composite material for sodium-ion battery cathode and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710652052.0A CN107394177B (en) | 2017-08-02 | 2017-08-02 | Nickel bicarbonate/graphene composite material for sodium-ion battery cathode and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107394177A CN107394177A (en) | 2017-11-24 |
CN107394177B true CN107394177B (en) | 2020-11-24 |
Family
ID=60343012
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710652052.0A Expired - Fee Related CN107394177B (en) | 2017-08-02 | 2017-08-02 | Nickel bicarbonate/graphene composite material for sodium-ion battery cathode and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107394177B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108054021B (en) * | 2017-12-07 | 2019-08-23 | 南阳理工学院 | Bicarbonate nickel-poly-dopamine-graphene composite material and preparation method and application |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103682277A (en) * | 2013-12-25 | 2014-03-26 | 南京师范大学 | N-doped carbon layer wrapped hollow-porous nickel oxide composite material and preparation method thereof |
CN103880093A (en) * | 2014-04-15 | 2014-06-25 | 山东大学 | Hollow spherical nickel bicarbonate aggregate |
CN104051729A (en) * | 2014-07-04 | 2014-09-17 | 电子科技大学 | Preparation method of NiFe2O4/graphene composite material for lithium battery cathode |
CN104795549A (en) * | 2015-03-20 | 2015-07-22 | 渤海大学 | Method for synthesizing graphene/nickel nano-composite material at room temperature |
CN105481026A (en) * | 2015-12-17 | 2016-04-13 | 宁波繁盛商业管理有限公司 | Preparation method of nickel bicarbonate |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101962211B (en) * | 2010-10-26 | 2013-07-17 | 南京工业大学 | Preparation method of nano nickel bicarbonate |
-
2017
- 2017-08-02 CN CN201710652052.0A patent/CN107394177B/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103682277A (en) * | 2013-12-25 | 2014-03-26 | 南京师范大学 | N-doped carbon layer wrapped hollow-porous nickel oxide composite material and preparation method thereof |
CN103880093A (en) * | 2014-04-15 | 2014-06-25 | 山东大学 | Hollow spherical nickel bicarbonate aggregate |
CN104051729A (en) * | 2014-07-04 | 2014-09-17 | 电子科技大学 | Preparation method of NiFe2O4/graphene composite material for lithium battery cathode |
CN104795549A (en) * | 2015-03-20 | 2015-07-22 | 渤海大学 | Method for synthesizing graphene/nickel nano-composite material at room temperature |
CN105481026A (en) * | 2015-12-17 | 2016-04-13 | 宁波繁盛商业管理有限公司 | Preparation method of nickel bicarbonate |
Non-Patent Citations (4)
Title |
---|
Interconnected Ni(HCO3)2 Hollow Spheres Enabled by Self-Sacrificial Templating with Enhanced Lithium Storage Properties;Shiqiang Zhao et al;《ACS Energy Lett.》;20161209;第2卷;摘要,补充信息的试验部分 * |
Reduced graphene oxide and nanosheet-based nickel oxide microsphere composite as an anode material for lithium ion battery;Xianjun Zhu et al;《Electrochimica Acta》;20120301;第64卷;全文 * |
Shiqiang Zhao et al.Interconnected Ni(HCO3)2 Hollow Spheres Enabled by Self-Sacrificial Templating with Enhanced Lithium Storage Properties.《ACS Energy Lett.》.2016,第2卷摘要,补充信息的试验部分. * |
Solvothermal synthesis of Ni(HCO3)2/graphene composites toward supercapacitors and the faradiac redox mechanism in KOH solution;Jinfeng Sun et al;《Journal of Alloys and Compounds》;20131231;第581卷;第218页实验部分,第220页左栏第1段 * |
Also Published As
Publication number | Publication date |
---|---|
CN107394177A (en) | 2017-11-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107394178B (en) | Cobalt carbonate/graphene composite material for sodium-ion battery cathode and preparation method and application thereof | |
CN105047919B (en) | Preparation method of lithium iron phosphate battery positive electrode material | |
CN112290022B (en) | Lithium ion battery anode lithium supplement additive and preparation method and application thereof | |
CN114864896A (en) | In-situ carbon-coated nano lithium iron phosphate cathode material and preparation method thereof | |
CN107317019B (en) | Ferrous carbonate/graphene composite material for sodium ion battery cathode and preparation method and application thereof | |
CN106992295B (en) | A kind of preparation method of monodisperse alpha-ferric oxide nanometer sheet | |
CN116014104A (en) | Lithium-rich nickel positive electrode material, preparation method thereof, positive electrode sheet and secondary battery | |
CN113772718B (en) | SnS-SnS 2 @ GO heterostructure composite material and preparation method and application thereof | |
CN101764217A (en) | Method for preparing nano-scale lithium iron phosphate | |
CN103400980A (en) | Iron sesquioxide/nickel oxide core-shell nanorod array film as well as preparation method and application thereof | |
CN108400296A (en) | Heterogeneous element doped ferroferric oxide/graphene negative material | |
CN103531789A (en) | Iron oxide-carbon nanotube ternary composite material and preparation method thereof | |
CN108400299B (en) | Preparation method of CuFe2O4/C composite anode material for sodium-ion battery | |
CN112694104B (en) | Prussian blue analogue, preparation method thereof, negative electrode material and application | |
CN103730664A (en) | Positive electrode material of lithium sulfur battery and preparation method and application of material | |
CN111384389A (en) | Precursor of ternary material | |
CN113410459A (en) | Embedded MoSxThree-dimensional ordered macroporous graphene carbon material of nanosheet, preparation and application | |
CN103441249B (en) | Lithium ion battery ternary cathode material modified by nanometer SnO2 and preparation method of lithium ion battery ternary cathode material | |
CN110600710B (en) | Iron sulfide-carbon composite material and preparation method thereof, lithium ion battery negative electrode material, lithium ion battery negative electrode piece and lithium ion battery | |
CN104124430A (en) | Ruthenium dioxide quantum dot modified vanadium pentoxide nano material as well as preparation method and application of material | |
CN107394177B (en) | Nickel bicarbonate/graphene composite material for sodium-ion battery cathode and preparation method and application thereof | |
CN114933292B (en) | Preparation method and application of lithium iron phosphate | |
CN109216692A (en) | Modified tertiary cathode material and preparation method thereof, lithium ion battery | |
CN114824221A (en) | Titanium dioxide coated CoSe 2 Base nano material and preparation method and application thereof | |
CN109987607B (en) | Mesoporous silicon/cobalt disilicide composite microsphere material and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201124 |
|
CF01 | Termination of patent right due to non-payment of annual fee |