CN111233054B - Copper-doped three-dimensional multilevel-structure nickel hydroxide material and preparation method and application thereof - Google Patents

Copper-doped three-dimensional multilevel-structure nickel hydroxide material and preparation method and application thereof Download PDF

Info

Publication number
CN111233054B
CN111233054B CN202010064888.0A CN202010064888A CN111233054B CN 111233054 B CN111233054 B CN 111233054B CN 202010064888 A CN202010064888 A CN 202010064888A CN 111233054 B CN111233054 B CN 111233054B
Authority
CN
China
Prior art keywords
copper
nickel hydroxide
hydroxide material
doped
solution
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.)
Active
Application number
CN202010064888.0A
Other languages
Chinese (zh)
Other versions
CN111233054A (en
Inventor
袁斌
张峻豪
李少波
胡仁宗
朱敏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN202010064888.0A priority Critical patent/CN111233054B/en
Publication of CN111233054A publication Critical patent/CN111233054A/en
Application granted granted Critical
Publication of CN111233054B publication Critical patent/CN111233054B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a copper-doped spherical multilevel-structure nickel hydroxide material and preparation and application thereof. The preparation method firstly prepares the NiSO4Aqueous solution with Na2S2O8Uniformly mixing; then adding concentrated ammonia water into the aqueous solution, uniformly mixing, then adding copper foil, and standing at room temperature for 24-40 h; and after the reaction is finished, centrifugally collecting a reaction product, washing the reaction product with water for several times, and then drying the product in vacuum to obtain the copper-doped spherical multilevel-structure nickel hydroxide material. The preparation method has strong controllability and simple operation, can be used for large-scale production of the electrode material of the lithium ion secondary battery, and can obviously prolong the cycle life of the electrode material.

Description

Copper-doped three-dimensional multilevel-structure nickel hydroxide material and preparation method and application thereof
Technical Field
The invention relates to nickel hydroxide (Ni (OH) with a three-dimensional multi-level structure stacked by nano sheets2) The material, the preparation method and the application belong to the field of nanometer functional materials and lithium ion secondary batteries.
Background
Lithium Ion Batteries (LIBs) are mainly composed of an anode, a cathode, an electrolyte, a diaphragm and the like. Li at charging+Extracted from the positive electrode, inserted into the negative electrode, and upon discharge, Li+Emerging from the negative electrode and fitting into the positive electrode, which is also known as a "rocking chair battery" because of the characteristics of lithium ion batteries.
The lithium ion battery is favored by researchers due to the advantages of high volume and mass energy density (high specific capacity), high output voltage (working voltage of 3.7V), low self-discharge, long service life and the like. One of the important factors affecting the energy output of lithium ion batteries is the specific capacity and voltage plateau of the positive electrode and the negative electrode, but the graphite negative electrode currently and commercially used is due to its low theoretical specific capacity (372mAh g)-1) Has become increasingly unable to meet the needs of the times, and materials with higher capacity are needed. Among the various alternative anode materials, nickel-based oxides (NiO) and their hydroxides (Ni (OH)2) Due to its considerable specific capacity (715 mAhg)-1And 576mAh g-1) Abundant resources, no toxicity and the like are widely concerned. However, nickel hydroxide cannot be popularized and applied because of its defects, including poor intrinsic conductivity, which causes large volume change during circulation, and finally causes material pulverization and shedding, and capacity rapid decay. The current methods for solving the problems mainly comprise nanocrystallization, multiphase compounding, doping for improving conductivity and structural stability and the like.
The nano-sizing limits the particle size of the material to nano level, which can reduce the absolute volume change of the material during lithium extraction and shorten Li+And (6) transferring the path. However, single nanocrystallization can cause material agglomeration, and meanwhile, the area of an SEI film can be increased due to the large specific surface area of the nanomaterial, so that more Li is generated+Loss, resulting in a first low coulombic efficiency and, in addition, a low stacking density.
The multiphase compounding means that a composite phase is constructed, an active material is compounded with other materials, a second phase comprises a buffer phase and is equal in conductivity, the improvement of the cycle performance of the battery by the measure is limited, and after a certain cycle number, the electrode material is inevitably pulverized and then loses efficacy.
Doping is also a commonly used method to improve the properties of electrode materials. The performance improvement of the doped material mainly comes from two aspects, namely the improvement of the conductivity and the structural stability. But the single doping measure can only improve the cycle performance of the material to a limited extent.
In summary, neither of the above methods alone can solve Ni (OH)2The cycle performance and rate capability of the negative electrode material are poor. The reason is that the performance of the anode material can only be improved to a certain extent by using the method alone, and the requirements of the anode material on huge volume change and electrode structural integrity in the long-term circulation process cannot be met.
CN2015101803613 discloses a hydrogen hydroxide for lithium ion batteryA preparation method of a nickel cathode material. Dissolving divalent nickel salt with distilled water to prepare a nickel salt solution; dissolving potassium hydroxide or sodium hydroxide with distilled water to prepare an alkali solution of potassium hydroxide or sodium hydroxide; controlling the reaction temperature to be 60 ℃, dropwise adding the alkali solution into the nickel salt solution under the stirring condition, and controlling the pH value of the reaction system to be 11.0; after the reaction is finished, the nickel hydroxide cathode material for the lithium ion battery is obtained after suction filtration, washing and freeze drying. Although the prepared nickel hydroxide has higher capacity, the first discharge capacity is 2237mAh g-1But at 100mA g-1Current density of (1) and only 1107mAh g is left after 30 times of circulation-1The capacity of (a) is poor, the cycle stability is poor, and the life of nickel hydroxide as a negative electrode of a lithium ion battery is not substantially improved.
Disclosure of Invention
In order to overcome Ni (OH)2The invention aims to provide a preparation method of a copper-doped nickel hydroxide material with a multilevel structure, which can effectively improve the cycling stability of nickel hydroxide used as a cathode material in a lithium ion battery.
With NiSO4Adding copper foil, ammonia water and Na in the reaction system as a nickel source2S2O8Preparing a new material made of Ni (OH)2The nano-sheets are elementary and can be assembled into Ni (OH) with micron-sized spherical structure2A material. The material is used as a lithium ion battery cathode material and can reinforce Li+And the transmission of electrons, relieve the volume change produced in the charge-discharge process, achieve the goal of improving the capacity, cycle performance and rate performance of the lithium ion battery.
In the invention, copper foil and Na are added into a reaction system2S2O8Can oxidize copper foil into copper ions, the concentration of the copper ions in the solution and Na2S2O8The amount is proportional. Copper ions can be doped as doping ions into the layered Ni (OH)2In the lithium ion battery, since the ionic radius of copper ions is larger than that of nickel ions, the interlayer spacing of nickel hydroxide can be stabilized and further increased, and Li in the process of lithium intercalation and deintercalation is increased+After second doping with copperThe nickel hydroxide will consist of beta-Ni (OH)2Conversion to alpha-Ni (OH)2The latter having a larger interlayer spacing with the formation of alpha-Ni (OH)2Is a nano sheet structure and is assembled into a micro spherical structure. The specific surface area of the micron-scale particles is smaller, so that an SEI film is formed less; the nanosheet layer contributes to Li+Rapid insertion and extraction of Li and shortening of Li+And the transmission distance of the electrons; the pores between the nanosheets help buffer the nano-alpha-Ni (OH)2The volume of the sheet layer is changed, the structural stability of the electrode material is enhanced, and the cycle stability of the electrode material is further improved. The invention relates to a multi-level micron spherical alpha-Ni (OH)2The material can better meet the requirement of being used as the lithium ion battery cathode material, the preparation process is simple, and the preparation is carried out at room temperature, so that external heating sources, such as hydrothermal conditions and the like, are not needed, the obvious energy-saving effect is achieved, and the large-scale production is more favorably realized.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the copper-doped spherical multilevel-structure nickel hydroxide material comprises the following steps:
(1) mixing NiSO4Dissolving in deionized water, stirring to obtain solution A, NiSO4The concentration is 0.5-1 mol/L;
(2) adding Na into the solution A obtained in the step (1) under stirring2S2O8Obtaining a solution B; wherein Na2S2O8With NiSO4The mass ratio of (A) to (B) is 0.12: 1-0.65: 1;
(3) adding ammonia water into the solution B obtained in the step (2) under stirring to obtain a solution C;
(4) adding excessive copper foil into the solution C obtained in the step (3), standing, and reacting for 24-40 hours at room temperature;
(5) and (4) after the reaction is finished, centrifugally collecting the reaction product obtained in the step (4), washing, and then carrying out vacuum drying on the reaction product to obtain the spherical multilevel-structure nickel hydroxide material.
To further achieve the object of the present invention, it is preferable that NiSO used in step (1) is4For analytical purification.
Preferably, the stirring in the steps (1), (2) and (3) is magnetic stirring, the rotating speed is 100-400 r/min, and the time is 12-18 min.
Preferably, the concentration of the ammonia water in the step (3) is 25-28%, and the volume of the ammonia water accounts for 8-15% of the volume of the deionized water in the step (1).
Preferably, the amount of the copper foil in the step (4) is Na2S2O8The mass of the copper is 40-100%, and redundant copper can be removed in the cleaning process.
Preferably, the copper foil in the step (4) is pure copper foil of a negative current collector of a commercial lithium ion battery, the thickness is 10 μm, and the purity is more than or equal to 99.8%.
Preferably, the washing in step (5) is washing with water 5 times or more.
Preferably, the vacuum drying in the step (5) is carried out at the temperature of 60-80 ℃, the drying time is 12-24 hours, and the vacuum degree of drying is 1000-4000 Pa.
The copper-doped spherical multilevel-structure nickel hydroxide material is prepared by the preparation method, and the basic unit of the spherical multilevel structure is made of nano-flake Ni (OH)2The diameter of the ball is 0.5-3 mu m, and the nano-flake Ni (OH)2The length and width ranges of the film are respectively 200-700 nm, and the thickness is 5-20 nm.
The spherical multilevel-structure nickel hydroxide material is prepared by doping nickel hydroxide with copper foil as a copper source and is applied to secondary battery electrode materials.
The principle of the invention is as follows: the main function of the added ammonia water is to react with Ni2+Forming nickel hydroxide which is capable of precipitating at room temperature without heating to hydrolyze the nickel salt to produce a precipitate, and adding the copper foil in Na2S2O8Can become Cu under strong oxidation2+alpha-Ni (OH) which is gradually doped in during the formation of nickel hydroxide and can consume part of ammonia water, lower the pH value of the system and promote2Formation (pH too high will become beta-Ni (OH))2) Furthermore, the nickel hydroxide nanosheets formed may stack into spheres as a result of the "directional bonding" growth process.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention can be realized by adding Na2S2O8The preparation method is used as an oxidant to realize the preparation of the spherical multilevel copper-doped nickel hydroxide material, and no additional step is needed after the reaction, so that the preparation method has the advantages of simple process, high efficiency and batch production.
(2) The invention can obtain the micron-sized anode material with controllable morphology by a simple one-step coprecipitation method, does not need other measures such as hydrothermal treatment and the like, saves energy and is simple and convenient to operate.
(3) Micron multilevel structure alpha-Ni (OH) prepared by the invention2The material is used as the lithium ion battery cathode, can effectively improve the volume expansion caused by long-term circulation, and improves the overall capacity, rate capability and cycle life of the lithium ion battery.
Drawings
FIG. 1 shows the case of example 1 without adding copper foil and Na2S2O8To obtain original beta-Ni (OH)2Sample with copper foil and Na added2S2O8The prepared spherical multilevel structure alpha-Ni (OH)2XRD diffractograms of copper-doped nickel hydroxide prepared for the samples and for different amounts of sodium persulfate added in example 2 and example 3.
The figure also includes alpha-Ni (OH)2(PDF #00-038-0715) and beta-Ni (OH)2(PDF #00-002-1112) standard XRD diffraction spectrum;
FIG. 2 shows the copper-doped spherical multilevel structure α -Ni (OH) of example 12And virgin beta-Ni (OH) without copper doping2SEM picture of (1); wherein, FIGS. 2(a) and 2(b) show the preparation of copper-doped spherical multilevel structure alpha-Ni (OH) by adding 1.5g of sodium persulfate in example 12SEM images of the sample at 20000 times and 10000 times magnification, respectively, FIGS. 2(c) and 2(d) are raw β -Ni (OH) without copper doping2SEM images of the samples at 20000 and 10000 times magnification, respectively;
FIG. 3 shows the copper-doped spherical multilevel structure α -Ni (OH) prepared by adding 1g (example 2) and 2.5g (example 3) of sodium persulfate2SEM picture of (1); wherein FIGS. 3(a) and 3(b) are examples2 copper-doped spherical multilevel structure alpha-Ni (OH) prepared by adding 1g of sodium persulfate2SEM images of sample at 20000 times and 10000 times magnification, respectively, and FIGS. 3(c) and 3(d) are the copper-doped spherical multilevel structure alpha-Ni (OH) prepared by adding 2.5g of sodium persulfate to example 32SEM images of the samples at 20000 and 10000 times magnification, respectively;
FIG. 4 shows the original β -Ni (OH) in example 12Sample (FIG. 4- (4)) and addition of 1.5g of sodium persulfate to prepare a copper-doped spherical multilevel structure alpha-Ni (OH)2Sample (FIG. 4- (1)) and example 2 with 1g of sodium persulfate added (FIG. 4- (2)) and example 3 with 2.5g of sodium persulfate added (FIG. 4- (3)) prepare copper-doped spherical multilevel structure alpha-Ni (OH)2A graph of the cycling performance of the sample at 1A/g current density for 630 cycles;
FIG. 5 shows original β -Ni (OH) in example 12Sample and copper doped, multi-stage, flower-like alpha-Ni (OH) prepared with 1.5g sodium persulfate addition2Sample and example 2 addition of 1g sodium persulfate and example 3 addition of 2.5g sodium persulfate to produce copper doped spherical multilevel structure alpha-Ni (OH)2A comparison graph of rate performance of the sample;
FIG. 6 shows the preparation of copper-doped spherical multilevel structure α -Ni (OH) by adding 1g of sodium persulfate in example 12Analyzing each element of the EDX energy spectrum of the sample;
FIG. 7 is a diagram showing the preparation of copper-doped spherical multilevel structure α -Ni (OH) by adding 1.5g of sodium persulfate in example 22Analyzing each element of the EDX energy spectrum of the sample;
FIG. 8 is a schematic diagram of the preparation of copper-doped spherical multilevel structure α -Ni (OH) by adding 2.5g of sodium persulfate in example 32And (3) analyzing each element of the EDX energy spectrum of the sample.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following examples and drawings, but the present invention is not limited thereto.
Example 1
(1) Will analyze pure NiSO4(6.8g) dissolved in deionized water (50mL) and magnetically stirred at 200 rpm for 15 minutes to give solution A;
(2) adding Na into the solution A obtained in the step (1) under magnetic stirring2S2O8(1.5g), stirring for 15 minutes to give solution B;
(3) under magnetic stirring, adding 5ml of concentrated ammonia water (25-28%) into the solution B obtained in the step (2), and stirring for 15 minutes to obtain a solution C;
(4) and (4) adding 1g of commercial lithium ion battery negative copper foil into the solution C obtained in the step (3), wherein the thickness is 10 microns, the purity is more than or equal to 99.8 percent, and standing for 24 hours at room temperature.
(5) After the reaction is finished, the reaction product obtained in the step (4) is collected by centrifugation and washed for 6 times by water, and then the reaction product is dried for 24 hours in vacuum at 60 ℃ under the vacuum degree of 1000 Pa.
The XRD diffraction pattern of the reaction product is shown in figure 1- (2), and the generated Ni (OH) is doped2The material is alpha-Ni (OH) with a hexagonal structure2Without addition of copper foil and Na2S2O8The product of (A) is beta-Ni (OH) of hexagonal structure2The XRD results correspond to those in FIG. 1- (1), and the pH value is lowered (in favor of the formation of. alpha. -Ni (OH)) because the added copper foil consumes a part of the ammonia water2) Meanwhile, as the ionic radius (73pm) of copper is larger than that (69pm) of nickel ions, after successful doping, the interlayer spacing of the material is increased to form alpha-Ni (OH)2. The basic unit of the reaction product is a nano-sheet structure, as shown in SEM image 2(a) at 20000 times, and each nano-sheet layer is assembled into a multi-stage spherical structure with a size of 0.5-3 μm, as shown in SEM image 2(b) at 10000 times, from which it is known that copper-doped α -Ni (OH) is prepared by adding 1.5g of sodium persulfate2And a plurality of gaps exist among the lamellar layers, so that the volume expansion is favorably relieved, wherein the length and the width of the lamellar Ni (OH)2 are respectively 200-700 nm, and the thickness is 5-20 nm. FIGS. 2(c) and 2(d) are SEM images of the original β -Ni (OH)2 sample without doped copper at 20000 times and 10000 times magnification, respectively, the powder morphology is mostly disordered and the agglomeration is severe. The two samples obtained above were subjected to energy spectrum analysis, and it can be seen from the data in Table 1 below in FIG. 6 that 1g of sodium persulfate was prepared so as to contain Ni, Cu, S, O in a proportion of 11.85% by mass of copper incorporated therein.
TABLE 1
Kind of element Atomic number Characteristic X-ray Mass percent of elements Atomic percent of element
Ni 28 K layer release of X-rays 49.95 26.11
O 8 K layer release of X-rays 32.89 63.08
Cu 29 K layer release of X-rays 11.85 5.72
S 16 K layer release of X-rays 5.31 5.08
In a glove box to prepare the spherical multilevel structure alpha-Ni (OH)2The material is a positive electrode, PE is a diaphragm, a metal lithium sheet is a negative electrode, ethylene carbonate is electrolyte, and the material is pressed into a button cell with the diameter of 12mm to form a half cell. The prepared half cell is subjected to charge and discharge performance test in a blue battery test system, and the specific parameters are as follows: the current density is 1A/g, and the charge-discharge voltage range is 0.01V-3V. As can be seen from the line (1) in fig. 4, the first discharge capacity reaches 1715.6mAh/g, the specific capacity after 630 cycles can be maintained at 1287.4mAh/g, and the capacity retention rate is about 75%; however, for the original beta-Ni (OH) produced2(FIG. 4- (4)), the first discharge capacity was 1292.8mAh/g, but the specific capacity after 630 cycles was reduced to 391.3mAh/g, and the capacity retention rate was only about 30%. In addition, the rate performance curve (figure 5) shows that the product after doping has more excellent rate performance from the current density of 100mA/g to 2000mA/g and then back to 100 mA/g.
Example 2
(1) Will analyze pure NiSO4(7.75g) dissolved in deionized water (50mL) and magnetically stirred at 400 rpm for 18 minutes to give solution A;
(2) adding Na into the solution A obtained in the step (1) under magnetic stirring2S2O8(1g) Stirring for 18 minutes to obtain a solution B;
(3) under magnetic stirring, adding 5ml of concentrated ammonia water (25-28%) into the solution B obtained in the step (2), and stirring for 18 minutes to obtain a solution C;
(4) and (4) adding 1g of commercial lithium ion battery negative copper foil into the solution C obtained in the step (3), wherein the thickness is 10 microns, the purity is more than or equal to 99.8 percent, and standing for 40 hours at room temperature.
(5) After the reaction is finished, the reaction product obtained in the step (4) is collected by centrifugation and washed by water for 8 times, and then the reaction product is dried for 12 hours in vacuum at 80 ℃ under the vacuum degree of 4000 Pa.
Reaction productThe material is also alpha-Ni (OH) with hexagonal structure2The XRD result corresponds to line (3) in fig. 1, the basic unit of the reaction product is a nano-platelet structure, and the individual nano-platelets assemble into a multi-level spherical structure of 0.5-3 μm size, as shown in fig. 3(a) and 3(b), which are SEM images at 20000 times and 10000 times magnification, respectively. The figure shows the appearance of the sample prepared by adding 1g of sodium persulfate, and more gaps exist among the sheet layers, which is favorable for relieving volume expansion, wherein the sheet Ni (OH)2The length and width ranges of the film are respectively 200-700 nm, and the thickness is 10-20 nm. When the material prepared by adding 1g of sodium persulfate was subjected to energy spectrum analysis, it was found from the data shown in FIG. 7 and Table 2 below that a sample prepared by adding 2g of sodium persulfate had Ni, Cu, S and O, and the percentage by mass of copper incorporated therein was 15.56%.
TABLE 2
Kind of element Atomic number Characteristic X-ray Mass percent of elements Atomic percent of element
Ni 28 K layer release of X-rays 46.07 24.01
O 8 K layer release of X-rays 33.31 63.68
Cu 29 K layer release of X-rays 15.56 7.49
S 16 K layer release of X-rays 5.06 4.83
In a glove box to prepare the spherical multilevel structure alpha-Ni (OH)2The material is a positive electrode, PE is a diaphragm, a metal lithium sheet is a negative electrode, ethylene carbonate is electrolyte, and the material is pressed into a button cell with the diameter of 12mm to form a half cell. The prepared half cell is subjected to charge and discharge performance test in a blue battery test system, and the specific parameters are as follows: the current density is 1A/g, and the charge-discharge voltage range is 0V-3V. As can be seen from the line (2) in FIG. 4, the first discharge capacity reaches 1682.5mAh/g, the specific capacity after 630 cycles can be kept at 999mAh/g, and the capacity retention rate is about 59.4%.
Example 3
(1) Will analyze pure NiSO4(3.875g) was dissolved in deionized water (50mL) and magnetically stirred at 100 rpm for 12 minutes to give solution A;
(2) adding Na into the solution A obtained in the step (1) under magnetic stirring2S2O8(2.5g), stirring for 12 minutes to obtain a solution B;
(3) under magnetic stirring, adding 5ml of concentrated ammonia water (25-28%) into the solution B obtained in the step (2), and stirring for 12 minutes to obtain a solution C;
(4) and (4) adding 1g of commercial lithium ion battery negative copper foil into the solution C obtained in the step (3), wherein the thickness is 10 microns, the purity is more than or equal to 99.8 percent, and standing for 30 hours at room temperature.
(5) After the reaction is finished, the reaction product obtained in the step (4) is collected by centrifugation and washed for 10 times by water, and then the reaction product is dried for 18 hours in vacuum at 70 ℃ under the vacuum degree of 2000 Pa.
The reaction product is alpha-Ni (OH) with hexagonal structure2The XRD result corresponds to fig. 1- (4), the basic unit of the reaction product is a nano-sheet structure, and each nano-sheet layer is assembled into a multi-level spherical structure with a size of 0.5-3 μm, as shown in fig. 3(c) and 3(d), which are SEM images at 20000 times and 10000 times, respectively, it can be known from the figure that the morphology of the sample prepared by adding 2.5g of sodium persulfate, there are many gaps between each sheet layer, which is good for relieving the volume expansion, wherein the sheet α -ni (oh)2The length and width ranges of the film are respectively 200-700 nm, and the thickness is 10-20 nm. The prepared sample to which 2.5g of sodium persulfate was added was subjected to energy spectrum analysis, and it was found from the data of FIG. 8 and Table 3 below that the sample prepared from 2.5g of sodium persulfate contained Ni, Cu, S, O in an amount of 21.11% by mass of copper incorporated therein.
TABLE 3
Kind of element Atomic number Characteristic X-ray Mass percent of elements Atomic percent of element
Ni 28 K layer release of X-rays 39.10 17.96
O 8 K layer release of X-rays 37.21 67.67
Cu 29 K layer release of X-rays 21.11 9.6
S 16 K layer release of X-rays 2.58 4.77
In a glove box to prepare the spherical multilevel structure alpha-Ni (OH)2The material is a positive electrode, PE is a diaphragm, a metal lithium sheet is a negative electrode, ethylene carbonate is electrolyte, and the material is pressed into a button cell with the diameter of 12mm to form a half cell. The prepared half cell is subjected to charge and discharge performance test in a blue battery test system, and the specific parameters are as follows: the current density is 1A/g, and the charge-discharge voltage range is 0V-3V. As can be seen from FIG. 4- (3), the first discharge capacity was 1520.5mAh/g, the specific capacity after 630 cycles was maintained at 900.4mAh/g (FIG. 4), and the capacity retention rate was about 59.2%.
The copper-doped nickel hydroxide prepared by the method has the potential of replacing a graphite cathode in a commercial lithium ion battery and realizing large-scale production.
Compared with the nickel hydroxide prepared in Chinese patent application 2015101803613, the cycle performance of the nickel hydroxide is obviously improved, and the first discharge capacity of the nickel hydroxide is 2237mAh g-1At 100mA g-1Current density of (1) and only 1107mAh g is left after 30 times of circulation-1The capacity of the nickel hydroxide is maintained at about 50 percent, and the first discharge capacity of the copper-doped nickel hydroxide prepared by the method reaches 1715.6mAh/g and is 1A g-1The specific capacity after 630 cycles can be kept at 1287.4mAh/g, and the capacity retention rate is about 75%.
The above-described embodiments are intended to be illustrative, rather than restrictive, and all such changes, modifications, substitutions, combinations, and simplifications that may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (9)

1. The preparation method of the copper-doped spherical multilevel-structure nickel hydroxide material is characterized by comprising the following steps of:
(1) mixing NiSO4Dissolving in deionized water, and stirring to obtain a solution A;
(2) adding Na into the solution A obtained in the step (1) under stirring2S2O8Obtaining a solution B; na (Na)2S2O8With NiSO4The mass ratio of (A) to (B) is 0.12: 1-0.65: 1;
(3) adding ammonia water into the solution B obtained in the step (2) under stirring to obtain a solution C;
(4) adding excessive copper foil into the solution C obtained in the step (3), standing, and reacting for 24-40 hours at room temperature;
(5) and (4) after the reaction is finished, centrifugally collecting the reaction product obtained in the step (4), washing, and drying in vacuum to obtain the spherical multilevel-structure spherical nickel hydroxide material.
2. The method for preparing a copper-doped spherical multilevel structure nickel hydroxide material according to claim 1, wherein the step (1)NiSO used in4For analytical purposes, NiSO4The concentration is 0.5 to 1 mol/L.
3. The method for preparing the copper-doped spherical multilevel-structure nickel hydroxide material according to claim 1, wherein the stirring in the steps (1), (2) and (3) is magnetic stirring, the rotating speed is 100-400 r/min, and the time is 12-18 min.
4. The method for preparing the copper-doped spherical multilevel-structure nickel hydroxide material according to claim 1, wherein the concentration of the ammonia water in the step (3) is 25-28%, and the volume of the ammonia water is 8-15% of the volume of the deionized water in the step (1).
5. The method for preparing the copper-doped spherical multilevel structure nickel hydroxide material according to claim 1, wherein the amount of the copper foil in the step (4) is Na2S2O840-100% of the mass; and redundant copper foil is removed when being cleaned after the reaction is finished, the copper foil is a commercial lithium ion battery negative copper current collector, the thickness is 10 mu m, and the purity is more than or equal to 99.8%.
6. The method for preparing the copper-doped spherical multilevel structure nickel hydroxide material according to claim 1, wherein the washing in the step (5) is performed 5 times or more with water.
7. The method for preparing the copper-doped spherical multilevel-structure nickel hydroxide material according to claim 1, wherein the vacuum drying temperature in the step (5) is 60-80 ℃, the drying time is 12-24 h, and the vacuum degree of drying is 1000-4000 Pa.
8. A copper-doped spherical multilevel-structure nickel hydroxide material is characterized by being prepared by the preparation method of any one of claims 1 to 7; the basic unit of the spherical multilevel structure consists of nano-sheet Ni (OH)2Composition of, in which the flake form Ni (OH)2Length and width ofRespectively 200-700 nm and 5-20 nm in thickness.
9. The use of the copper-doped spherical multilevel structure nickel hydroxide material according to claim 8 in an electrode material for a secondary battery.
CN202010064888.0A 2020-01-20 2020-01-20 Copper-doped three-dimensional multilevel-structure nickel hydroxide material and preparation method and application thereof Active CN111233054B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010064888.0A CN111233054B (en) 2020-01-20 2020-01-20 Copper-doped three-dimensional multilevel-structure nickel hydroxide material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010064888.0A CN111233054B (en) 2020-01-20 2020-01-20 Copper-doped three-dimensional multilevel-structure nickel hydroxide material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN111233054A CN111233054A (en) 2020-06-05
CN111233054B true CN111233054B (en) 2021-06-08

Family

ID=70872838

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010064888.0A Active CN111233054B (en) 2020-01-20 2020-01-20 Copper-doped three-dimensional multilevel-structure nickel hydroxide material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111233054B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113120973B (en) * 2021-03-31 2022-03-18 海南大学 Preparation method of copper-doped nickel-aluminum layered double hydroxide, obtained product and application

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6042753A (en) * 1996-10-06 2000-03-28 Matsushita Electric Industrial Co., Ltd. Active materials for the positive electrode in alkaline storage batteries
JPH11250903A (en) * 1998-02-26 1999-09-17 Hitachi Maxell Ltd Nickel hydrogen storage battery
CN105070512B (en) * 2015-08-06 2017-11-17 太原理工大学 Mix the flower-shaped α Ni (OH) of Mg nanometer sphericals2Electrode material and preparation method thereof
CN105543846A (en) * 2016-02-05 2016-05-04 广东成德电子科技股份有限公司 Neutral etching agent for printed circuit board and etching method

Also Published As

Publication number Publication date
CN111233054A (en) 2020-06-05

Similar Documents

Publication Publication Date Title
CN107681118A (en) Iron nickel secondary batteries negative plate and preparation method thereof and the iron nickel secondary batteries using the negative plate
CN101958411B (en) CoO-Co composite material with core-shell structure and preparation method thereof
CN111017958A (en) Preparation method of nano spherical Prussian blue compound
CN108063239B (en) Preparation method of sodium-ion battery electrode material with net structure
CN110993971B (en) NiS 2 /ZnIn 2 S 4 Composite material and preparation method and application thereof
CN110620270B (en) Secondary copper-zinc battery
CN111233054B (en) Copper-doped three-dimensional multilevel-structure nickel hydroxide material and preparation method and application thereof
CN110790248A (en) Iron-doped cobalt phosphide microsphere electrode material with flower-like structure and preparation method and application thereof
CN103811741A (en) Castanea-shaped hollow micro-sphere formed by surrounding of vanadium oxide nano wire as well as preparation method and application of micro-sphere
CN112018355B (en) Preparation method of three-dimensional rod-shaped potassium titanate material
CN115332507B (en) Carbon-coated sodium iron phosphate composite electrode material and preparation and application thereof
CN109205671B (en) From VS2Preparation method and application of graded-structure ball composed of nanosheets
CN111129461A (en) Preparation method of lithium manganate ternary composite material
CN114975920B (en) Electrode material of core-shell structure graphite alkyne coated with metallic antimony, and preparation method and application thereof
CN111129443A (en) Composite ternary cathode material, preparation method thereof and lithium ion battery
CN114243007A (en) Nickel disulfide/carbon nanotube composite electrode material and preparation method and application thereof
CN110707290B (en) Preparation method of flexible lithium ion battery negative electrode with sandwich-like structure
CN114361421A (en) Polyanion type high-voltage sodium-ion battery positive electrode material and preparation method thereof
CN115231554B (en) Preparation method of self-synthesized nano silicon-carbon composite material
CN117525307B (en) Alkaline battery cathode material and preparation method and application thereof
CN114864889B (en) Metal oxide-carbon composite material with carbon point regulated and controlled as well as preparation method and application thereof
CN114864903B (en) Graphene-based selenium positive electrode material embedded with two-dimensional metal selenide, preparation method of graphene-based selenium positive electrode material and lithium-selenium battery
CN114684800B (en) Method for preparing three-dimensional phosphorus-rich compound by combining electrostatic spinning method and low-temperature phosphating method, electrode material and potassium ion battery
CN111153441B (en) Preparation method of potassium cobaltate particles
CN106920956A (en) The preparation method of cryogenic carbon cladded type acid lithium titanate

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