CN105280915A - Preparation method for lithium battery positive electrode material lithium nickel manganese oxide - Google Patents

Preparation method for lithium battery positive electrode material lithium nickel manganese oxide Download PDF

Info

Publication number
CN105280915A
CN105280915A CN201510611361.4A CN201510611361A CN105280915A CN 105280915 A CN105280915 A CN 105280915A CN 201510611361 A CN201510611361 A CN 201510611361A CN 105280915 A CN105280915 A CN 105280915A
Authority
CN
China
Prior art keywords
lithium
source
mineralizer
nickel
preparation
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.)
Granted
Application number
CN201510611361.4A
Other languages
Chinese (zh)
Other versions
CN105280915B (en
Inventor
朱国斌
曲群婷
郑洪河
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.)
Jiangsu win win Technology Co., Ltd.
Original Assignee
Suzhou University
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 Suzhou University filed Critical Suzhou University
Priority to CN201510611361.4A priority Critical patent/CN105280915B/en
Publication of CN105280915A publication Critical patent/CN105280915A/en
Application granted granted Critical
Publication of CN105280915B publication Critical patent/CN105280915B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • H01M4/48—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
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a preparation method for a lithium battery positive electrode material lithium nickel manganese oxide. The preparation method comprises the following steps of (a), adding a lithium source, a nickel source and a manganese source into a solvent to be dissolved and mixed to obtain a first mixed solution, wherein the molar ratio of the lithium source to the nickel source to the manganese source is 10:5:9; (b), adding an oxidant and a mineralizing agent into the first mixed solution, and then moving the mixed solution to an autoclave, and reacting at the temperature of 150-230 DEG C for 48-72 hours; and (c), grinding the product obtained from the step (b) into powder and pressuring into flake-shaped, and then heating processed product in the air atmosphere at the temperature of 800-950 DEG C for 12-24 hours to obtain the lithium battery positive electrode material lithium nickel manganese oxide, wherein the mineralizing agent comprises a main mineralizing agent; the main mineralizing agent is KOH or/and NaOH; the molar ratio of the main mineralizing agent to the nickel source is 60-180:5; and the molar ratio of the oxidant to the nickel source is 6:5. The preparation method for the lithium battery positive electrode material lithium nickel manganese oxide is simple in synthetic process, low in cost, easy to control experiment conditions and convenient to realize the industrial production of the lithium nickel manganese oxide.

Description

A kind of preparation method of anode material of lithium battery nickel ion doped
Technical field
The invention belongs to anode material of lithium battery field, relate to a kind of preparation method of nickel ion doped, be specifically related to a kind of preparation method of anode material of lithium battery nickel ion doped.
Background technology
The progress of positive electrode and optimization promote the key of lithium ion battery technology to safety, environmental protection, low cost, high-energy-density and high power density future development.Extensively the positive electrode of investigation and application mainly contains the LiMO of layer structure at present 2the LiMn of (M=Co, Ni, Mn), spinel structure 2o 4and LiFePO 4, but this several positive electrode all has respective shortcoming, LiCoO 2scarcity of resources, cost are high, toxicity is large; LiNiO 2preparation condition is harsh, thermally-stabilised difference; LiMn 2o 4theoretical capacity is not high, and dissolves and Jahn-Teller effect due to manganese, causes the cyclical stability of material circulation performance especially under high temperature to be greatly affected, LiFePO 4extremely low electronic conductivity and ionic conductivity have impact on the chemical property of material.
Transient metal doped spinelle LiMn 2-xm xo 4positive electrode (wherein M=Ni, Co, Cr, Cu, Fe, Al, Zn, Mg, Ti etc.) current potential high (reaching about 5V), energy density are high, are referred to as 5V level anode material for lithium-ion batteries.At these 5V level spinelles LiMn 2-xm xo 4in positive electrode, LiMn 1.5ni 0.5o 4have higher discharge capacity (theoretical specific capacity can reach 147mAh/g), discharge voltage is high and steady (almost only having single 4.7V platform), based on the energy density of the lithium ion battery of this positive electrode than traditional spinelle LiMn 2o 4improving more than 30%, is most promising anode material for lithium-ion batteries of future generation.At spinelle LiMn 1.5ni 0.5o 4in, Mn, Ni are respectively+4 and+divalent, and material corresponds to Ni at the discharge platform of 4.7V 2+/ Ni 4+, owing to there is not Mn in material in redox reaction 3+, Mn wherein 4+do not participate in electrode reaction, therefore, this material can not occur due to Mn in electrochemistry cyclic process 3+disproportionated reaction and cause the dissolving of Mn, meanwhile, owing to there is no Mn 3+existence, spinelle LiMn 1.5ni 0.5o 4also John-Teller effect can not occur, these all contribute to the long-term cycle performance realizing electrode undoubtedly.Moreover, due to LiMn 1.5ni 0.5o 4in spinel structure, the bond energy (1029Kj/mol) of Ni-O key is obviously greater than the bond energy (946Kj/mol) of Mn-O key, and this also contributes to the cyclical stability improving material.From the viewpoint of these, spinelle LiMn 1.5ni 0.5o 4alternative traditional spinelle LiMn 2o 4the ideal chose of positive electrode.
At present, restricting the key factor that this material is successfully applied to lithium ion battery has two: one to be Mn 3+interference, preparation LiMn 1.5ni 0.5o 4process in, high-temperature firing easily causes the oxygen in spinel structure to lack, and occurs unnecessary Mn in material 3+, particularly under high―temperature nuclei condition (﹥ 800 DEG C), in material, also easily there is Ni 3+and Li xni 1-xo impurity phase, Mn 3+and Ni 3+existence not only make the 4V level platform of material disappear completely, and make material phase transformation in charge and discharge process serious, chemical property worsens, and accelerates the inducing capacity fading in cyclic process.Doped with metal elements can stabilizing material lattice framework, eliminate spinelle LiMn 1.5ni 0.5o 4in Mn 3+interference, this is because doped with the valence state being beneficial to raising or stable Mn, eliminates the Mn in material 3+and Li xni 1-xo dephasign, suppresses John-Teller effect.Current Mg, Al, Ti, Cr, Ce, Cu, Fe, Zn, Co, Mo plasma is all used to prepare Li doped Mn 1.5ni 0.5o 4positive electrode, although doping can reduce material internal Mn 3+amount, eliminate 4V level discharge platform and extend life-span of material, but the specific capacity of material also can be caused to decline.With regard to current Li doped Mn 1.5ni 0.5o 4the research situation of material, people to doped metallic elements for improving LiMn 1.5ni 0.5o 4the research of material is a lot, but large to the blindness of doped chemical selection, lacks scientific and design.Two is that the high-rate charge-discharge capability of material is bad, as the positive electrode of power lithium-ion battery of future generation, and spinelle LiMn 1.5ni 0.5o 4high rate performance comparatively spinelle LiMn 2o 4difference, this directly affects the charge and discharge power of battery undoubtedly, restricts its application in electrokinetic cell.
The main cause affecting material rate charge-discharge performance has two: one to be the electron conduction of material, electron conduction directly affects the rate charge-discharge performance of material, but not determine the most critical factor of this material high rate performance, because electron conduction can method be improved by adding conductive agent and carbon is coated etc.Two is material internal Li diffusion rates, and electrochemical impedance test shows, spinelle LiMn 1.5ni 0.5o 4body mutually in the diffusion coefficient D of lithium ion only 10 -13cm 2s -1on the order of magnitude, than commercialization spinelle LiMn 2o 4the low 2 number magnitude of diffusion coefficient of middle lithium ion, lithium ion is departed from electrode process for this or to embed the resistance of intracell large, and electrochemical polarization phenomenon is obvious.
LiNi 0.5mn 1.5o 4can be synthesized by multiple method, comprise solid-phase synthesis, sol-gal process, hydro thermal method, molte-salt synthesis, ultrasonic spray pyrolysis, carbonate method and coprecipitation etc.The LiNi that different synthetic methods obtains 0.5mn 1.5o 4there is significant difference in the performance of spinel.Such as, it is simple that traditional solid-phase synthesis has technique, and preparation condition holds manageable advantage, low for equipment requirements, is convenient to suitability for industrialized production, is a kind of preparation method that current suitability for industrialized production anode material for lithium-ion batteries mainly uses.But, the LiNi of this method synthesis 0.5mn 1.5o 4uneven components, reactant does not fully contact, and easily produces impurity, and discharge capacity is lower.Sol-gal process can the LiNi of production uniform component 0.5mn 1.5o 4, product particle is nanoscale.But this synthetic method complex steps, cost is high, is difficult to large-scale promotion application, is generally limited to the sample preparation in laboratory.Recently, solid phase method combines with sol-gal process by the people such as Lee cleverly, proposes carbonate method.They use (NH 4) 2cO 3, precipitate Ni simultaneously 2+and Mn 2+obtain the mixed precipitation of Ni, Mn carbonate of uniform component, then by sedimentation and filtration, washing, dry, mix with LiOH, ball milling, then roasting, obtain the LiNi of spinel structure 0.5mn 1.5o 4.This method not only substantially reduces the process of the loaded down with trivial details time-consuming evaporating solvent in sol-gel process, and can prepare the product of uniform component.But, cause the loss and waste of raw material in the process of precipitation, more seriously can change final products LiNi 0.5mn 1.5o 4the ratio of middle Ni, Mn.
Meanwhile, existing hydro thermal method has been widely used and synthetic material, but also there is many weak points.Surfactant and template use the cost and the complexity that add material, and point one-step hydrothermal extends the cycle of experiment, and the preparation of presoma adds the uncontrollability of experiment, and cause the material profile of synthesis irregular, granularity is uneven.On reaction condition, many factors can affect hydro-thermal reaction simultaneously, shows as the uncontrollability of reaction condition.On chemical property, outstanding behaviours is that discharge capacity is lower when high-multiplying power discharge.Therefore, be badly in need of in prior art solving these technical problems, prepared by LiNi to hydro thermal method 0.5mn 1.5o 4optimize.
Summary of the invention
The present invention seeks to the preparation method that a kind of anode material of lithium battery nickel ion doped is provided to overcome the deficiencies in the prior art.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of anode material of lithium battery nickel ion doped, and it comprises the following steps:
A lithium source, nickel source and manganese source join in solvent to dissolve and are mixed to get the first mixed solution by (), the mol ratio in described lithium source, nickel source and manganese source is 10:5:9;
B () added oxidant and mineralizer in described first mixed solution, transferred in autoclave subsequently, in 150 ~ 230 DEG C of reactions 48 ~ 72 hours;
C (), by the product grind into powder in step (b), is pressed into sheet, then in air atmosphere, in 800 ~ 950 DEG C of heating 12 ~ 24h;
Described mineralizer comprises main mineralizer; Described main mineralizer be KOH or/and NaOH, the mol ratio in itself and nickel source is 60 ~ 180:5; The mol ratio in described oxidant and nickel source is 6:5, and described oxidant is that potassium permanganate is or/and potassium manganate.
Optimally, described mineralizer is made up of main mineralizer and auxiliary mineralizer, the mass ratio of described main mineralizer and described auxiliary mineralizer or mol ratio are 60 ~ 180:5 ~ 15, and described auxiliary mineralizer is the mixture of one or more compositions in lithium carbonate, lithium acetate and lithium hydroxide.
Optimally, described lithium source is the mixture of one or more compositions in lithium carbonate, lithium acetate and lithium hydroxide.
Optimally, described nickel source is the mixture of one or more compositions in nickelous sulfate, nickel acetate, nickel nitrate and nickel oxide.
Optimally, described manganese source is the mixture of one or more compositions in manganese nitrate, manganese acetate, manganese sulfate.
Optimally, described solvent is deionized water, ethanol, acetone, ethanol-acetone solution or ethylene glycol.
Further, described main mineralizer is KOH, and described auxiliary mineralizer is lithium acetate.
Because technique scheme is used, the present invention compared with prior art has following advantages: the preparation method of anode material of lithium battery nickel ion doped of the present invention, mineralizer and oxidant dissolving and mixing is become owner of by adding in the solution to lithium source, nickel source and manganese source, calcine under being placed in high temperature, air after first carrying out hydro-thermal reaction again, the method synthesis technique is simple, cost is low, easily-controlled experimental conditions, is convenient to the suitability for industrialized production realizing nickel ion doped; Obtained nickel ion doped uniform particles, average grain diameter about 1 μm, shortens the diffusion length of lithium ion in material, adds the contact area of material and electrolyte, drastically increase the electrochemical kinetics of material; And degree of crystallinity is high, impurity is few, improves the initial discharge specific capacity of material.
Accompanying drawing explanation
Accompanying drawing 1 is the X-ray diffraction spectrum of anode material of lithium battery nickel ion doped of the present invention: (a) embodiment 4, (b) embodiment 3, (c) embodiment 2, (d) embodiment 1, (e) comparative example 1;
Accompanying drawing 2 is the SEM figure of anode material of lithium battery nickel ion doped of the present invention: (a) embodiment 7, (b) embodiment 8, (c) embodiment 1, (d) embodiment 9;
Accompanying drawing 3 is the X-ray diffraction spectrum of anode material of lithium battery nickel ion doped of the present invention: (a) embodiment 7, (b) embodiment 8, (c) embodiment 1, (d) embodiment 9;
Accompanying drawing 4 is LiNi obtained in embodiment 9 0.5mn 1.5o 4material changes into the voltage-capacity curve chart of two circles at 0.1C;
Accompanying drawing 5 is LiNi obtained in embodiment 9 0.5mn 1.5o 4material is at the discharge capacity figure of different multiplying;
Accompanying drawing 6 is LiNi obtained in embodiment 9 0.5mn 1.5o 4material cyclic discharge capacity figure.
Embodiment
The preparation method of anode material of lithium battery nickel ion doped of the present invention, it comprises the following steps: lithium source, nickel source and manganese source join in solvent to dissolve and be mixed to get the first mixed solution by (a), and the mol ratio in described lithium source, nickel source and manganese source is 10:5:9; B () added oxidant and mineralizer in described first mixed solution, transferred in autoclave subsequently, in 150 ~ 230 DEG C of reactions 48 ~ 72 hours; C (), by the product grind into powder in step (b), is pressed into sheet, then in air atmosphere, in 800 ~ 950 DEG C of heating 12 ~ 24h; Described mineralizer comprises main mineralizer; Described main mineralizer be KOH or/and NaOH, the mol ratio in itself and nickel source is 60 ~ 180:5; The mol ratio in described oxidant and nickel source is 6:5, and described oxidant is that potassium permanganate is or/and potassium manganate.Mineralizer and oxidant dissolving and mixing is become owner of by adding in the solution to lithium source, nickel source and manganese source, calcine under being placed in high temperature, air after first carrying out hydro-thermal reaction again, the method synthesis technique is simple, and cost is low, easily-controlled experimental conditions, is convenient to the suitability for industrialized production realizing nickel ion doped; Obtained nickel ion doped uniform particles, average grain diameter about 1 μm, shortens the diffusion length of lithium ion in material, adds the contact area of material and electrolyte, drastically increase the electrochemical kinetics of material; And degree of crystallinity is high, impurity is few, improves the initial discharge specific capacity of material.And oxidant plays the effect of two aspects, one is carry out mensuration oxidation to manganese source, avoids high-temperature firing to cause the oxygen in spinel structure to lack, eliminates Mn 3+interference; Himself be reduced rear as manganese source, reduce the consumption in manganese source, saved cost.
Described mineralizer is preferably made up of main mineralizer and auxiliary mineralizer, the mass ratio of described main mineralizer and described auxiliary mineralizer or mol ratio are 60 ~ 180:5 ~ 15, and described auxiliary mineralizer is the mixture of one or more compositions in lithium carbonate, lithium acetate and lithium hydroxide.In main mineralizer, add auxiliary mineralizer create beyond thought effect: auxiliary mineralizer provide not only extra lithium source, can also regulate the crystal structure of nickel ion doped, thus improves the high rate performance of nickel ion doped.Described lithium source is preferably the mixture of one or more compositions in lithium carbonate, lithium acetate and lithium hydroxide.Described nickel source is preferably the mixture of one or more compositions in nickelous sulfate, nickel acetate, nickel nitrate and nickel oxide.Described manganese source is preferably the mixture of one or more compositions in manganese nitrate, manganese acetate, manganese sulfate.Described solvent is preferably deionized water, ethanol, acetone, ethanol-acetone solution or ethylene glycol.Described main mineralizer is preferably KOH, and described auxiliary mineralizer is preferably lithium acetate.
Below in conjunction with accompanying drawing embodiment, the present invention is further described.
Embodiment 1
The present embodiment provides a kind of preparation method of anode material of lithium battery nickel ion doped, and it comprises the following steps:
A 0.01mol lithium acetate, 0.005mol nickel acetate and 0.009mol manganese acetate join in solvent to dissolve and are mixed to get the first mixed solution by ();
B () added 0.006mol oxidant and mineralizer (being made up of 0.01mol lithium acetate and 0.06molKOH) in described first mixed solution, transferred to subsequently in autoclave, in 150 DEG C of reactions 72 hours;
C (), by the product grind into powder in step (b), is pressed into sheet, then in air atmosphere, in 800 DEG C of heating 24h.
Embodiment 2
The present embodiment provides a kind of preparation method of anode material of lithium battery nickel ion doped, basically identical in its preparation process and embodiment 1, and the component unlike mineralizer is different, and it is made up of 0.01mol lithium acetate and 0.12molKOH.
Embodiment 3
The present embodiment provides a kind of preparation method of anode material of lithium battery nickel ion doped, basically identical in its preparation process and embodiment 1, and the component unlike mineralizer is different, and it is made up of 0.01mol lithium acetate and 0.18molKOH.
Embodiment 4
The present embodiment provides a kind of preparation method of anode material of lithium battery nickel ion doped, basically identical in its preparation process and embodiment 1, and the component unlike mineralizer is different, and it is made up of 0.01mol lithium acetate and 0.24molKOH.
Embodiment 5
The present embodiment provides a kind of preparation method of anode material of lithium battery nickel ion doped, basically identical in its preparation process and embodiment 1, concrete technology parameter is inconsistent, is specially: 0.01mol lithium acetate, 0.005mol nickel acetate and 0.009mol manganese acetate join in solvent to dissolve and be mixed to get the first mixed solution by (a);
B () added 0.006mol oxidant and mineralizer (being made up of 0.01mol lithium acetate and 0.06molKOH) in described first mixed solution, transferred to subsequently in autoclave, in 230 DEG C of reactions 48 hours;
C (), by the product grind into powder in step (b), is pressed into sheet, then in air atmosphere, in 950 DEG C of heating 12h.
Embodiment 6
The present embodiment provides a kind of preparation method of anode material of lithium battery nickel ion doped, basically identical in its preparation process and embodiment 1, concrete technology parameter is inconsistent, is specially: 0.01mol lithium acetate, 0.005mol nickel acetate and 0.009mol manganese acetate join in solvent to dissolve and be mixed to get the first mixed solution by (a);
B () added 0.006mol oxidant and mineralizer (being made up of 0.01mol lithium acetate and 0.06molKOH) in described first mixed solution, transferred to subsequently in autoclave, in 200 DEG C of reactions 55 hours;
C (), by the product grind into powder in step (b), is pressed into sheet, then in air atmosphere, in 900 DEG C of heating 18h.
Embodiment 7
The present embodiment provides a kind of preparation method of anode material of lithium battery nickel ion doped, basically identical in its preparation process and embodiment 2, unlike: in step (b), not containing 0.01mol lithium acetate in mineralizer.
Embodiment 8
The present embodiment provides a kind of preparation method of anode material of lithium battery nickel ion doped, basically identical in its preparation process and embodiment 2, unlike: in step (b), in mineralizer, the mole of lithium acetate is 0.005mol.
Embodiment 9
The present embodiment provides a kind of preparation method of anode material of lithium battery nickel ion doped, basically identical in its preparation process and embodiment 2, unlike: in step (b), in mineralizer, the mole of lithium acetate is 0.015mol, and its performance is shown in Fig. 4 to Fig. 6.
Embodiment 10
The present embodiment provides a kind of preparation method of anode material of lithium battery nickel ion doped, basically identical in its preparation process and embodiment 2, unlike, lithium source, nickel source and manganese source are respectively: lithium carbonate, nickelous sulfate, manganese acetate.
Comparative example 1
The present embodiment provides a kind of preparation method of anode material of lithium battery nickel ion doped, basically identical in its preparation process and embodiment 2, unlike: not containing KOH in mineralizer.
Nickel ion doped in embodiment 1 to 9 is made into lithium battery anode, detailed process is: by positive electrode nickel ion doped, acetylene black, PVDF in 8:1:1(mass ratio) ratio be dispersed in a certain amount of nmp solvent, under the rotating speed of 10000rpm, half an hour is stirred with high-speed shearing machine, after slurry fully mixes, coating machine is coated with, puts into 60 DEG C of baking ovens dry; After dry, pole piece thickness is 50 ~ 60nm, and pole piece is depressed into 75% of original depth by recycling roll squeezer, and being washed into diameter is after the circular pole piece of 13mm, puts into 120 DEG C of dry 16h of vacuum drying oven, then puts into glove box.
In the glove box being full of argon shield gas, with the LiNi of above-mentioned making 0.5mn 1.5o 4pole piece as positive pole, using lithium sheet as negative pole, the LiPF of 1mol/L 6being dissolved in (volume ratio 1:1:1) in EC/EMC/DMC solvent is electrolyte, and Celgard2500 polypropylene screen (purchased from American Celgard company) is barrier film, is assembled into button cell; And electro-chemical test is carried out on the electric battery charging and discharging tester (purchased from Wuhan Land Electronic Co., Ltd.) of indigo plant.
In formation process, use the current density constant current charge of C/10 to 4.9V, then use the current density constant-current discharge of C/10 to 3.5V, formation process continues three circles.During loop test, with 1C rate charge-discharge 200 times.During multiplying power test, battery, with the charging of 0.1C multiplying power, encloses in 0.1C, 0.2C, 0.5C, 1.0C, 2.0C, 5.0C, 10.0C, 20.0C different multiplying electric discharge 3 respectively.
The amount of KOH in mineralizer that controls directly determines the pH value of solution, and the pH of solution increases along with KOH amount and increases, as can be seen from Figure 1 when the amount of KOH be 0 or 0.24mol time do not form LiNi 0.5mn 1.5o 4, when the amount of KOH is 0, can find out that the product that reaction generates is Mn from XRD collection of illustrative plates 3o 4; When the amount of KOH reaches 0.24mol, do not form crystal.Along with the increase of KOH amount, the degree of crystallinity of sample increases, and lattice constant significantly reduces.
Embodiment 7, embodiment 8, embodiment 1 and embodiment 9 add different proportion to assist mineralizer LiAc, generate product and be respectively B1, B2, B3, B4, its XRD diffracting spectrum as shown in Figure 3, when the ratio of LiAc is respectively 0,5, when 10 and 15, the diffraction maximum of products therefrom is all very sharp-pointed, and sample all has good crystallinity, and the product of generation is LiNi 0.5mn 1.5o 4, the diffraction peak intensity of sample B2 is the highest, and crystallization is best.Sample increases by 0,5,10 along with LiAc ratio gradually at the diffraction peak intensity of 42 ° ~ 50 °, as shown in Figure 3; When the LiAc ratio added is 15, there will be the diffraction maximums of 44.3 ° and move to left.According to XRD diffraction pattern, the lattice constant that we calculate gained sample B1, B2, B3, B4 is respectively 8.19228,8.17744,8.17285,8.20005.Can draw thus, along with the increase of LiAc amount, the lattice constant of gained sample reduces.When the LiAc amount added reaches a certain value, the lattice constant of gained sample increases.When the LiAc ratio added departs from 10, its cell parameter obviously increases, and this illustrates Mn 3+content increases.As shown in Figure 2, obviously, the spinel structure of B1-B4 material is remarkable, and granular size is comparatively even, and average grain diameter is about 1 μm for the SEM figure of material B 1-B4; Wherein the dispersiveness of sample B1, B2 particle is better, and agglomeration is few, and sample particle is uniformly dispersed, and presents polyhedral structure clearly, shows that its degree of crystallinity is higher.Along with the raising granular size change of LiAc amount is little, but agglomeration increases the weight of to some extent, and when the amount of LiAc reaches 0.015mol, agglomeration is alleviated to some extent.
To sum up, there is being closely connected in the auxiliary amount of mineralizer LiAC and the physical property of sample, along with the increase of LiAc amount, the degree of crystallinity of sample is first deteriorated and improves, and lattice constant first reduces to become large again; The amount of auxiliary mineralizer LiAC also with the electrochemical properties close relation of sample, in embodiment 9 synthesis material when 1C charge and discharge cycles first discharge capacity be 100.3mAh/g, after circulation 200 circle, capability retention is 98.70%, and time under high magnification 20C, discharge capacity is 95.5mAh/g.
Above-described embodiment is only for illustrating technical conceive of the present invention and feature; its object is to person skilled in the art can be understood content of the present invention and implement according to this; can not limit the scope of the invention with this; all equivalences done according to Spirit Essence of the present invention change or modify, and all should be encompassed within protection scope of the present invention.

Claims (7)

1. a preparation method for anode material of lithium battery nickel ion doped, is characterized in that, it comprises the following steps:
A lithium source, nickel source and manganese source join in solvent to dissolve and are mixed to get the first mixed solution by (), the mol ratio in described lithium source, nickel source and manganese source is 10:5:9;
B () added oxidant and mineralizer in described first mixed solution, transferred in autoclave subsequently, in 150 ~ 230 DEG C of reactions 48 ~ 72 hours;
C (), by the product grind into powder in step (b), is pressed into sheet, then in air atmosphere, in 800 ~ 950 DEG C of heating 12 ~ 24h;
Described mineralizer comprises main mineralizer; Described main mineralizer be KOH or/and NaOH, the mol ratio in itself and nickel source is 60 ~ 180:5; The mol ratio in described oxidant and nickel source is 6:5, and described oxidant is that potassium permanganate is or/and potassium manganate.
2. the preparation method of anode material of lithium battery nickel ion doped according to claim 1, it is characterized in that: described mineralizer is made up of main mineralizer and auxiliary mineralizer, the mass ratio of described main mineralizer and described auxiliary mineralizer or mol ratio are 60 ~ 180:5 ~ 15, and described auxiliary mineralizer is the mixture of one or more compositions in lithium carbonate, lithium acetate and lithium hydroxide.
3. the preparation method of anode material of lithium battery nickel ion doped according to claim 1, is characterized in that: described lithium source is the mixture of one or more compositions in lithium carbonate, lithium acetate and lithium hydroxide.
4. the preparation method of anode material of lithium battery nickel ion doped according to claim 1, is characterized in that: described nickel source is the mixture of one or more compositions in nickelous sulfate, nickel acetate, nickel nitrate and nickel oxide.
5. the preparation method of anode material of lithium battery nickel ion doped according to claim 1, is characterized in that: described manganese source is the mixture of one or more compositions in manganese nitrate, manganese acetate, manganese sulfate.
6. the preparation method of anode material of lithium battery nickel ion doped according to claim 1, is characterized in that: described solvent is deionized water, ethanol, acetone, ethanol-acetone solution or ethylene glycol.
7. the preparation method of anode material of lithium battery nickel ion doped according to claim 2, is characterized in that: described main mineralizer is KOH, and described auxiliary mineralizer is lithium acetate.
CN201510611361.4A 2015-09-23 2015-09-23 A kind of preparation method of anode material of lithium battery nickel ion doped Active CN105280915B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510611361.4A CN105280915B (en) 2015-09-23 2015-09-23 A kind of preparation method of anode material of lithium battery nickel ion doped

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510611361.4A CN105280915B (en) 2015-09-23 2015-09-23 A kind of preparation method of anode material of lithium battery nickel ion doped

Publications (2)

Publication Number Publication Date
CN105280915A true CN105280915A (en) 2016-01-27
CN105280915B CN105280915B (en) 2017-06-16

Family

ID=55149543

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510611361.4A Active CN105280915B (en) 2015-09-23 2015-09-23 A kind of preparation method of anode material of lithium battery nickel ion doped

Country Status (1)

Country Link
CN (1) CN105280915B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108649217A (en) * 2018-05-09 2018-10-12 哈尔滨工业大学（威海） A kind of preparation method of high-voltage lithium-battery cathode material bat mixing nickel ion doped
CN111943283A (en) * 2020-08-13 2020-11-17 松山湖材料实验室 Positive electrode active material, preparation method thereof, secondary battery positive electrode and lithium battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101640266A (en) * 2009-09-01 2010-02-03 深圳市贝特瑞新能源材料股份有限公司 Preparation method of high-voltage anode material of lithium ion batteries
CN103227323A (en) * 2013-05-22 2013-07-31 哈尔滨工业大学 Preparation method of positive pole material (spinel type lithium nickel manganese oxide) of high-voltage lithium ion battery
US20140099559A1 (en) * 2012-10-05 2014-04-10 Ut-Battelle, Llc Coating compositions for electrode compositions and their methods of making
CN105118983A (en) * 2015-09-16 2015-12-02 湖北宇电能源科技股份有限公司 Method for preparing lithium nickel manganese oxide anode material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101640266A (en) * 2009-09-01 2010-02-03 深圳市贝特瑞新能源材料股份有限公司 Preparation method of high-voltage anode material of lithium ion batteries
US20140099559A1 (en) * 2012-10-05 2014-04-10 Ut-Battelle, Llc Coating compositions for electrode compositions and their methods of making
CN103227323A (en) * 2013-05-22 2013-07-31 哈尔滨工业大学 Preparation method of positive pole material (spinel type lithium nickel manganese oxide) of high-voltage lithium ion battery
CN105118983A (en) * 2015-09-16 2015-12-02 湖北宇电能源科技股份有限公司 Method for preparing lithium nickel manganese oxide anode material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108649217A (en) * 2018-05-09 2018-10-12 哈尔滨工业大学（威海） A kind of preparation method of high-voltage lithium-battery cathode material bat mixing nickel ion doped
CN108649217B (en) * 2018-05-09 2021-09-28 哈尔滨工业大学（威海） Preparation method of high-voltage lithium battery anode material bat mixed lithium nickel manganese oxide
CN111943283A (en) * 2020-08-13 2020-11-17 松山湖材料实验室 Positive electrode active material, preparation method thereof, secondary battery positive electrode and lithium battery

Also Published As

Publication number Publication date
CN105280915B (en) 2017-06-16

Similar Documents

Publication Publication Date Title
Santhanam et al. High rate cycling performance of Li1. 05Ni1/3Co1/3Mn1/3O2 materials prepared by sol–gel and co-precipitation methods for lithium-ion batteries
Kang et al. Preparation and electrochemical performance of yttrium-doped Li [Li0. 20Mn0. 534Ni0. 133Co0. 133] O2 as cathode material for lithium-ion batteries
Yi et al. Enhanced rate performance of molybdenum-doped spinel LiNi0. 5Mn1. 5O4 cathode materials for lithium ion battery
Luo et al. Effects of synthesis conditions on the structural and electrochemical properties of layered Li [Ni1/3Co1/3Mn1/3] O2 cathode material via the hydroxide co-precipitation method LIB SCITECH
Liu et al. Fluorine doping and Al2O3 coating Co-modified Li [Li0. 20Ni0. 133Co0. 133Mn0. 534] O2 as high performance cathode material for lithium-ion batteries
CN109873140B (en) Graphene composite ternary cathode material of lithium ion battery and preparation method of graphene composite ternary cathode material
CN109301207B (en) Surface layer doped with Ce3+And the surface layer is coated with CeO2NCM ternary cathode material and preparation method thereof
CN101308926B (en) Lithium ionic cell composite positive pole material coated by orthosilicate and its preparation method
CN104600285A (en) Method for preparing spherical lithium nickel manganese oxide positive pole material
Cong et al. (PO4) 3− polyanions doped LiNi1/3Co1/3Mn1/3O2: an ultrafast-rate, long-life and high-voltage cathode material for Li-ion rechargeable batteries
CN105024067B (en) Lithium ion battery, composite doped modified positive active material thereof and preparation method
Yi et al. High-performance xLi2MnO3·(1-x) LiMn1/3Co1/3Ni1/3O2 (0.1⿤ x⿤ 0.5) as Cathode Material for Lithium-ion Battery
CN104538623A (en) Preparation method for sphere-like lithium nickel manganese oxide positive electrode material
CN103311532A (en) Preparation method of lithium-enriched anode material with nano-grade lamellar-spinel composite structure
Zhang et al. High-rate layered lithium-rich cathode nanomaterials for lithium-ion batteries synthesized with the assist of carbon spheres templates
CN102623691A (en) Method for preparing lithium nickel manganese oxide serving as cathode material of lithium battery
CN103441263B (en) The method of a kind of collosol and gel-solid sintering technology synthesis nickle cobalt lithium manganate
CN102263238A (en) Lithium nickel cobalt manganese oxide and preparation method thereof
CN113880147B (en) Preparation method for reducing voltage drop of positive electrode material, positive electrode material and application
Zhu et al. Controlling the oxygen deficiency for improving the insertion performance of the layered LiNi0. 6Co0. 2Mn0. 2O2
Luo et al. Enhancing the electrochemical performance of Co-less Ni-rich LiNi0. 925Co0. 03Mn0. 045O2 cathode material via Co-modification with Li2B4O7 coating and B3+ doping
Zhang et al. Ce-doped LiNi 1/3 Co (1/3− x/3) Mn 1/3 Ce x/3 O 2 cathode materials for use in lithium ion batteries
CN102820463B (en) Doping lithium-rich manganese-based anode material and preparation method thereof, lithium ion battery
Wang et al. Preparation and performance of Mg-doped spinel-structured LiMn2O4 cathode materials
Huang et al. Effect of sintering temperature on the electrochemical performance of Li-rich Mn-basfed cathode material Li1. 2Mn0. 54Ni0. 13Co0. 13O2 by co-precipitation method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20170830

Address after: 211400 Yizheng Province Economic Development Zone, Yangzhou, Fujian Province, the Thai Road, No. 1, No.

Patentee after: Jiangsu win win Technology Co., Ltd.

Address before: Suzhou City, Jiangsu province 215137 Xiangcheng District Ji Road No. 8

Patentee before: Soochow University

TR01 Transfer of patent right