CN106887583B - A kind of positive electrode and its preparation method and application - Google Patents

A kind of positive electrode and its preparation method and application Download PDF

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CN106887583B
CN106887583B CN201510937404.8A CN201510937404A CN106887583B CN 106887583 B CN106887583 B CN 106887583B CN 201510937404 A CN201510937404 A CN 201510937404A CN 106887583 B CN106887583 B CN 106887583B
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spinel
positive electrode
preparation
shell
nickel ion
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CN106887583A (en
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曹安民
朴俊宇
万立骏
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • 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

Abstract

The invention discloses a kind of positive electrodes and its preparation method and application, are spinel-type nickel ion doped LiNi0.5Mn1.5O4‑δ(0≤δ < 0.1), it has the metallic element gradually decreased from the inside doping concentration in surface, it is greater than 0 shell so as to form close with inner core and close connection thickness, the doping of metallic element accounts for percentage composition x≤10wt% of spinel-type nickel ion doped weight.The present invention is using the method for controlled precipitation in nickel ion doped surface basis weight deposited metal element, heat treatment is recycled to permeate metallic element internally from nickel ion doped surface, shell is formed in kernel nickel ion doped surface in situ, the structural similarity of shell and kernel is very high, the problem of compatibility is good, and nucleocapsid removing has been solved perfectly.The presence of shell significantly improves the stability of thermal stability of the positive electrode in charge and discharge process, cyclical stability and material self structure, has very high practicability application prospect in energy storage field.

Description

A kind of positive electrode and its preparation method and application
Technical field
The invention belongs to lithium ion battery material technical fields, in particular to a kind of positive electrode and its preparation side Method and application.
Background technique
As a kind of reliable, efficient energy storage device, lithium ion battery since the advent of the world just establishes what it can not shake Status.Wherein, core of the positive electrode as lithium ion battery is always the emphasis of scientific research personnel's concern.It is currently used just Pole material, is limited to its lower energy density and higher price, and performance cannot still allow user satisfied.Thus, high-energy The research and development of density positive electrode have extremely important realistic meaning.
By the spinel-type nickel ion doped developed on the basis of LiMn2O4, operating voltage is up to 4.7V (vs.Li/Li+), More electric energy can be stored under identical capacity.And its energy density is higher than common cobalt acid lithium, LiMn2O4 and phosphoric acid Iron lithium.Three-dimensional lithium ion diffusion admittance present in spinel structure, has been effectively ensured the high power performance of material, has considered further that Its preparation process is simple, and raw material is cheap and easy to get, it is believed that nickel ion doped is that one kind is quite having the power battery of application prospect just Pole material.
Unmodified nickel ion doped material haves the defects that some to be difficult to overcome.Such as in charge and discharge process, due to nickel manganese Sour lithium operating voltage is higher, and with electrolyte side reaction can occur for electrode surface, consumes Li+, cause effective lithium to reduce, capacity attenuation Seriously.In addition, in nickel ion doped crystal, often there is Mn3+, the Mn of material surface3+Easily disproportionation generates Mn2+And it is dissolved in electrolysis In liquid, material surface is caused to be destroyed, ultimately causes material capacity decaying.
Studies have shown that can effectively inhibit material surface by introducing one layer of stable shell on nickel ion doped surface Side reaction improves the structural stability of material.Currently, the most common mode for constructing stable shell is exactly coating modification.Wherein, The substances such as zinc oxide, aluminium oxide, aluminum fluoride are most commonly seen coverings.But the lithium ionic mobility of these substances and electricity Electron conductivity is often bad, and the high rate performance of material often becomes negatively affected.Moreover, the shell constructed by the method coated Layer, since shell is entirely different with inner core, due to volume change when charge and discharge, the phenomenon that being easy to appear removing. It is then desired to find more reasonable means to construct core-shell structure.
Summary of the invention
The present invention is intended to provide a kind of positive electrode and its preparation method and application, this method deposition process is controllable, and can Forming one layer in the surface in situ of kernel spinel-type nickel ion doped has metallic element to adulterate and determine the finishing coat of thickness (also referred to as doped layer or shell), to obtain a kind of spinel-type nickel lithium manganate cathode material of novel core-shell structure, the shell The presence of layer can significantly improve the steady of thermal stability of the material in charge and discharge process, cyclical stability and material self structure It is qualitative.
To achieve the goals above, the present invention provides a kind of positive electrode, which is spinel-type nickel mangaic acid Lithium LiNi0.5Mn1.5O4-δ(0≤δ < 0.1), have in the spinel-type nickel ion doped inwardly adulterate from surface concentration gradually Reduce ground metallic element, so as to form doped layer close and close-connected with inner core, also referred to as shell, the shell Thickness is greater than 0, and the doping of the metallic element accounts for percentage composition x≤10wt% of spinel-type nickel ion doped weight；It is preferred that Ground, 0 < x≤5wt%；It is highly preferred that 0 < x≤2wt%；It is further preferred that 0.29≤x≤0.89wt%；It is further excellent Selection of land, 0.56≤x≤0.62wt%.
Further, shell with a thickness of 1~50nm；Preferably 1~30nm；More preferably 10~25nm, such as can be with For 15nm or 20nm.
Further, the metallic element is selected from one of Mg, Ca, Al, Ti, Fe, Co, Cu, Zn, Zr or a variety of.
The present invention also provides a kind of methods for preparing above-mentioned positive electrode, the described method comprises the following steps:
(1) by raw material spinel-type nickel ion doped LiNi0.5Mn1.5O4-δ(0≤δ < 0.1), the presoma of doping metals In a solvent with precipitating reagent dispersion, regulator is added to adjust the pH value of reaction system to 1.5~7.0, heating stirring reaction makes The presoma that must be introduced is converted into the solid-phase compound containing the doped metallic elements, and uniform deposition is in the spinelle The surface of type nickel ion doped, separates after the reaction was completed, washs, dry, obtains intermediate product；
(2) intermediate product is ground uniformly, calcining is cooled to room temperature, obtains the positive electrode.
Further, reaction described in step (1) is precipitating-heat leak reaction of metal ion；The solvent be water or Ethyl alcohol.
Further, precipitating reagent described in step (1) is carbonate, bicarbonate, formates, acetate, hydrophosphate With one of phosphate or a variety of.Further, precipitating reagent is selected from ammonium hydrogen carbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, carbon Potassium hydrogen phthalate, potassium carbonate, ammonium formate, ammonium acetate, formamide, acetamide, urea, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, tricresyl phosphate One of ammonium, disodium-hydrogen, sodium dihydrogen phosphate, sodium phosphate, potassium phosphate,monobasic, potassium dihydrogen phosphate and potassium phosphate are a variety of； The further preferably mixture of diammonium hydrogen phosphate and ammonium formate, ammonium formate, sodium bicarbonate or urea.
Further, presoma described in step (1) is selected from chlorate, sulfate, nitrate, the perchloric acid of metallic element At least one of salt, acetate and alkoxide；It is preferred that the metallic element can be Mg, Ca, Al, Ti, Fe, Co, Cu, Zn, Zr One of or it is a variety of；The presoma for example can be ANN aluminium nitrate nonahydrate, ferric chloride hexahydrate, acetic acid dihydrate zinc or titanium One of sour four butyl esters are a variety of.
Further, regulator is added in step (1) to adjust the pH value of the reaction system to 2.0~5.5；More preferably It is 3.0~5.0；Regulator is selected from formic acid, acetic acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, ammonium hydroxide, sodium hydroxide and potassium hydroxide One of.
Further, the temperature that is stirred to react in step (1) is 20~95 DEG C, preferably 30~80 DEG C；Further preferably 45~90 DEG C；Reaction time is 2~4 hours.Such as it can be stirred 2 hours at 45 DEG C；Or it is stirred 2 hours at 50 DEG C； Or it is stirred 4 hours at 90 DEG C；Or it is stirred 4 hours at 90 DEG C.
Further, in the reaction system of step (1), the concentration of raw material spinel-type nickel ion doped is 0.01g/L ~1000g/L, preferably 0.1g/L~100g/L, further preferably 1g/L~80g/L, more preferably 20~50g/L.It is described The concentration of presoma is 1 × 10-6Mol/L~0.1mol/L；It is preferred that 1 × 10-5Mol/L~0.01mol/L；Further preferably 1 ×10-4Mol/L~1 × 10-3mol/L.The concentration of the precipitating reagent is 1 × 10-6Mol/L~10mol/L, preferably 1 × 10- 5Mol/L~1mol/L.
Further, in step (2), 200~1200 DEG C of calcinings 1~10 are warming up to 1~50 DEG C/min of heating rate Hour；Preferably, 450~800 DEG C are warming up to 3~15 DEG C/min of heating rate, calcined 3~4 hours.
Invention further provides a kind of electrodes comprising above-mentioned positive electrode.
Invention further provides a kind of batteries comprising above-mentioned electrode.
Beneficial effects of the present invention:
The present invention deposits metallic element in spinel-type nickel ion doped surface basis weight using the method for controlled precipitation, then benefit Permeate metallic element internally from spinel-type nickel ion doped surface with heat treatment, in this way in kernel spinel-type nickel manganese The surface in situ of sour lithium forms spinel-type nickel ion doped finishing coat (the also referred to as doped layer or shell of one layer of metallic element doping Layer).The present invention carries out special metallic element by the surface to spinel-type nickel lithium manganate cathode material particle and modifies, thus The spinel-type nickel ion doped electrode material for having a kind of novel core-shell structure is obtained, kernel is spinel-type nickel mangaic acid Lithium, i.e. LiNi0.5Mn1.5O4-δ(0≤δ < 0.1), shell are the spinel-type nickel ion doped doped layer of metallic element doping.This hair The spinel-type nickel ion doped electrode material of the core-shell structure of bright preparation, very due to the structural similarity of its shell and kernel Height, compatibility is good, thus the problem of nucleocapsid removing has been solved perfectly.The presence of the shell can significantly improve material in charge and discharge The stability of thermal stability in the process, cyclical stability and material self structure, has very high reality in energy storage field With property application prospect.
The preparation method of the spinel-type nickel ion doped electrode material provided by the invention for having new type structure of hud, effectively Ground combines the advantages of cladding is with both modification modes are adulterated in the prior art, is a kind of effective surface doping side of stabilization Method.Specifically, this method can under the premise of not influencing material overall performance passivating material surface, hence it is evident that it is rotten to reduce surface Erosion and surface side reaction, and can efficiently solve shell and the problem of kernel is removed in cyclic process.Meanwhile the present invention Surface doping method, prepared by high-performance kernel and stablized the spinel-type of novel core-shell structure that shell constitutes Nickel ion doped material, this applies the extensive maturation of nickel ion doped material, has extremely real meaning.
Detailed description of the invention
Fig. 1 is the transmission electron microscope of the spinel-type nickel ion doped for the core-shell structure that the surfaces of aluminum of embodiment 1 is adulterated Photo；
Fig. 2 is the EDS test result of the spinel-type nickel ion doped for the core-shell structure that the surfaces of aluminum of embodiment 1 is adulterated；
Fig. 3 is the spherical aberration correction electronic display of the spinel-type nickel ion doped for the core-shell structure that the surfaces of aluminum of embodiment 1 is adulterated Micro mirror photo；And
Fig. 4 is the spinel-type nickel ion doped charge and discharge under 2C multiplying power for the core-shell structure that the surfaces of aluminum of embodiment 1 is adulterated Cycle performance.
Specific embodiment
As described above, being spinel-type nickel ion doped LiNi the present invention provides a kind of positive electrode0.5Mn1.5O4-δ(0 ≤ δ < 0.1), have in the spinel-type nickel ion doped inwardly adulterate from surface ground concentration gradually decrease metallic element, from And doped layer close and close-connected with inner core is formd, also referred to as shell, the thickness of the shell is greater than 0, the gold The doping for belonging to element accounts for percentage composition x≤10wt% of the spinel-type nickel ion doped weight；Preferably, 0 < x≤ 5wt%；It is highly preferred that 0 < x≤2wt%；It is further preferred that 0.29≤x≤0.89wt%；It is further preferred that 0.56 ≤ x≤0.62wt%.
The present invention passes through in spinel-type nickel ion doped LiNi0.5Mn1.5O4-δThe surface doping of (0≤δ < 0.1) is specific Metallic element has obtained the doped layer (i.e. shell) with passivated surface, hence it is evident that reduce surface corrosion and surface side reaction Generation, and due to being to form shell in the surface in situ of kernel, thus the structure of shell and inner core are highly similar, have Effect ground solves the problems, such as that shell and kernel are removed during circulating battery, has obtained by high-performance kernel and has stablized shell structure At novel core-shell structure spinel-type nickel ion doped material.
According to the present invention, shell with a thickness of 1~50nm；Preferably 1~30nm；More preferably 10~25nm.Such as also It can be 15nm or 20nm.The present invention can during the preparation process by control doping metals presoma sedimentation time and The parameters such as subsequent calcination temperature and time control the thickness of shell.
The present invention also provides a kind of preparation methods of above-mentioned positive electrode, comprising the following steps:
(1) by raw material spinel-type nickel ion doped LiNi0.5Mn1.5O4-δ(0≤δ < 0.1), doping metals presoma and Precipitating reagent is dispersed in solvent (solvent can be water or ethyl alcohol)；Regulator is added later to adjust the pH value of reaction system To 1.5~7.0, heating stirring is reacted, so that the presoma introduced is converted into the immobilization containing the doped metallic elements Object is closed, and uniform deposition separates after the reaction was completed on the surface of the spinel-type nickel ion doped, washed, it is dry, obtain centre Product.
(2) intermediate product of step (1) is ground uniformly, calcining is cooled to room temperature, obtains positive electrode of the invention.
It is to contain the doped metallic elements for the ease of realization is described using the precursor form of the doped metallic elements Solid-phase compound carry out quantitative, uniform deposition on the surface of kernel spinel-type nickel ion doped.The presoma is selected from metal At least one of chlorate, sulfate, nitrate, perchlorate, acetate and alkoxide of element.It is preferred that metallic element can be with For one of Mg, Ca, Al, Ti, Fe, Co, Cu, Zn, Zr or a variety of.Such as presoma can be ANN aluminium nitrate nonahydrate, six water Close one of iron chloride, acetic acid dihydrate zinc or butyl titanate etc. or a variety of.
According to the present invention, in step (1), the pH value of reaction system is adjusted to 1.5~7.0, if mainly too in view of pH It is low, it is possible to biggish injury be caused to material, therefore the pH of initial reaction system is adjusted to suitable range.
According to the present invention, in step (1), after the pH value for adjusting reaction system, heating and stirring to reaction system makes it It reacts.Preferably, being stirred to react temperature is 20~95 DEG C；More preferably 30~80 DEG C；Further preferably 45~90 DEG C. The reaction time is 2~4 hours.Such as it can be stirred 2 hours at 45 DEG C；Or it is stirred 2 hours at 50 DEG C；Or It is stirred 4 hours at 90 DEG C.It is reacted by heating stirring so that the presoma introduced is converted into and contains the doped metallic elements Solid-phase compound and uniform deposition on the surface of spinel-type nickel ion doped.It to be separated after the reaction was completed, washs, does It is dry, obtain intermediate product.
According to the present invention, in the reaction system of step (1), the concentration of raw material spinel-type nickel ion doped is 0.01g/ L~1000g/L, preferably 0.1g/L~100g/L, further preferably 1g/L~80g/L, more preferably 20~50g/L.If The concentration of raw material is too high, will lead to deposition it is too fast, may cause intermediate product synthesis failure.If the concentration of raw material is too Low, the product that will lead to primary first-order equation synthesis is very few.
Wherein, the concentration of the presoma is 1 × 10-6Mol/L~0.1mol/L；It is preferred that 1 × 10-5Mol/L~ 0.01mol/L；Further preferably 1 × 10-4Mol/L~1 × 10-3mol/L.If the excessive concentration of presoma, will lead to and mix Miscellaneous amount is excessively high, influences the performance of positive electrode；If the concentration of presoma is too low, it will lead to intermediate product and be difficult to be formed, influence Adulterate success rate.
Wherein, the concentration of the precipitating reagent is 1 × 10-6Mol/L~10mol/L, preferably 1 × 10-5Mol/L~1mol/ L.If the excessive concentration of precipitating reagent, it is too fast to will lead to metallic element deposition, causes doping uneven；On the contrary, if precipitating reagent Concentration is too low, will lead to that metallic element deposition is too low, to cause the doping of metallic element in positive electrode too low, equally It will affect the performance of positive electrode.
According to the present invention, in step (2), heating after the grinding uniformly of intermediate product obtained in step (1) is calcined, it is excellent Choosing is warming up to 200~1200 DEG C with 1~50 DEG C/min of heating rate and calcines 1~10 hour.More preferably with 3~15 DEG C/min Heating rate be warming up to 450~800 DEG C, calcine 3~4 hours.In view of the height of calcination temperature and the length of calcination time The short success rate for influencing whether doping and doping depth, therefore, through comprehensively considering, the present invention preferably will heat up rate, calcining temperature Degree and time control are in above-mentioned range.
Invention further provides a kind of electrodes comprising above-mentioned positive electrode.
Invention further provides a kind of batteries comprising above-mentioned electrode.
Below in conjunction with drawings and examples, the present invention is described in further detail.But skilled in the art realises that Protection scope of the present invention is not limited only to following embodiment.According to the present disclosure, those skilled in the art will recognize that To in the case where not departing from technical characteristic given by technical solution of the present invention and range, embodiment described above is made perhaps More change and modification belong to protection scope of the present invention.
Embodiment 1
1, the nuclear-shell structure type nickel ion doped of preparation surfaces of aluminum doping
By spinel-type nickel ion doped LiNi in flask0.5Mn1.5O4-δThe presoma of (0≤δ < 0.1) powder 0.5g, aluminium ANN aluminium nitrate nonahydrate 20mg, precipitating reagent diammonium hydrogen phosphate 10mg, precipitating reagent ammonium formate 2g are dispersed in 30ml water, obtain reactant System.In the reaction system, the concentration of the spinel-type nickel ion doped is 16.7g/L；The ANN aluminium nitrate nonahydrate it is dense Degree is 1.8 × 10-3mol/L；The concentration of the diammonium hydrogen phosphate is 2.5 × 10-3The concentration of mol/L, the ammonium formate is 1.06mol/L。
Regulator hydrochloric acid is added into reaction system to adjust the pH to 3 of the reaction system, is stirred to react 2 at 45 DEG C Hour, through centrifugation, washs, is dried to obtain intermediate product.
Intermediate product is warming up to 800 DEG C with 4 DEG C/min of rate, calcines 3 hours, is cooled to later at this temperature Room temperature obtains the spinel-type nickel ion doped powder of the core-shell structure of surfaces of aluminum doping.Its kernel is spinel-type nickel ion doped LiNi0.5Mn1.5O4-δ(0≤δ < 0.1), the doping of the aluminium in shell are the 0.29wt.% of spinel-type nickel ion doped.
Fig. 1 is the transmitted electron of the spinel-type nickel ion doped of the core-shell structure of the doping of surfaces of aluminum obtained in embodiment 1 Microscope photo, it can be seen that the surface of nickel ion doped variation without exception.This illustrates the spinel-type nickel of the core-shell structure of preparation The kernel of manganate cathode material for lithium and good, the not excessive architectural difference of the compatibility of shell, i.e. structure height are similar.
Fig. 2 is that the EDS of the spinel-type nickel ion doped of the core-shell structure of the doping of surfaces of aluminum obtained in embodiment 1 tests knot Fruit.It can be seen that Al element is gradually decreased from the concentration that surface is inwardly adulterated, the thickness for adulterating the shell of Al is about 10nm.
Fig. 3 is the spherical aberration correction of the spinel-type nickel ion doped of the core-shell structure of the doping of surfaces of aluminum obtained in embodiment 1 Electron micrograph.It can be seen that surface doped region (round frame) is different with kernel (box) Atomic Arrangement, this explanation exists Material surface forms doped layer (also referred to as shell).
2, the electrode of the spinel-type nickel ion doped of the core-shell structure of preparation surfaces of aluminum doping
The spinel-type nickel ion doped powder 0.24g for the core-shell structure for taking the surfaces of aluminum of above-mentioned preparation to adulterate, adds with conduction Agent super-p is added (to provide) 0.03g, binder PVDF (Kynoar) by Hefei company, Ke Jing Materials Technology Ltd. 0.03g and a little solvent NMP (N-Methyl pyrrolidone) mixing is obtained through slurrying, smear (aluminium foil is as collector), drying The spinel-type nickel ion doped electrode of the core-shell structure of surfaces of aluminum doping.
3, assembled battery
The spinel-type nickel ion doped electrode of the core-shell structure adulterated using surfaces of aluminum obtained in above-mentioned steps 2 is as just Pole is assembled into battery with cathode of lithium, and electrolyte selects concentration for the carbonic ester electrolyte of 1M, wherein solvent are as follows: DMC (carbonic acid two Methyl esters): DEC (diethyl carbonate): EC (ethylene carbonate)=1:1:1 (W/W), solute are 1.0M LiPF6。
4, battery testing
Constant current charge-discharge test is carried out to above-mentioned battery using storage battery charge/discharge tester, test voltage section is 3.0 ~5.0V, test temperature are 25 DEG C.Battery capacity and charging and discharging currents are with the spinel-type of the core-shell structure of surfaces of aluminum doping The Mass Calculation of nickel ion doped.
The cycle performance of Fig. 4 battery charge and discharge under 2C multiplying power of material thus.Battery holds by 100 circle circulations, battery Amount basically no attenuation, remains at 115mAh/g or so, and coulombic efficiency 100%, has good capacity retention ratio, longevity substantially Life and coulombic efficiency.
Embodiment 2
1, the nuclear-shell structure type nickel ion doped of surface Fe2O3 doping is prepared
By spinel-type nickel ion doped LiNi in flask0.5Mn1.5O4-δThe presoma of (0≤δ < 0.1) powder 0.5g, iron Ferric chloride hexahydrate 15mg, precipitating reagent ammonium formate 2g are dispersed in 30ml water, obtain reaction system.In the reaction system, The concentration of the spinel-type nickel ion doped is 16.7g/L；The concentration of the ferric chloride hexahydrate is 1.9 × 10-3mol/L；Institute The concentration for stating ammonium formate is 1.06mol/L.
Regulator nitric acid is added into reaction system to adjust the pH to 2.0 of the reaction system, it is small that 2 are stirred at 50 DEG C When, through centrifugation, washs, is dried to obtain intermediate product.
Intermediate product is warming up to 800 DEG C with 3 DEG C/min of rate, calcines 3 hours at this temperature, obtains Surface Fe The spinel-type nickel ion doped powder of the core-shell structure of doping.Its kernel is spinel nickel LiMn2O4 LiNi0.5Mn1.5O4-δ(0≤δ < 0.1), the Fe2O3 doping amount of shell is the 0.62wt% of spinel nickel LiMn2O4.The thickness of shell is about 25nm.
2, the electrode of the spinel-type nickel ion doped of the core-shell structure of surface Fe2O3 doping is prepared
By the spinel-type nickel ion doped powder 0.24g of the core-shell structure of the surface Fe2O3 doping of above-mentioned preparation and conductive addition Agent super-p 0.03g, binder PVDF (Kynoar) 0.03g and a little solvent NMP mixing, through slurrying, smear (aluminium foil As collector), it is dry, obtain the spinel-type nickel ion doped electrode of the core-shell structure of surface Fe2O3 doping.
3, assembled battery
Using the spinel-type nickel ion doped electrode of the core-shell structure of surface Fe2O3 doping obtained in above-mentioned steps 2 as just Pole is assembled into battery with cathode of lithium, and electrolyte selects concentration for the carbonic ester electrolyte of 1M, wherein solvent are as follows: DMC:DEC:EC =1:1:1 (W/W), solute are 1.0M LiPF6。
4, battery testing
Constant current charge-discharge test is carried out to above-mentioned battery using storage battery charge/discharge tester, test voltage section is 3.0 ~5.0V, test temperature are 25 DEG C.Battery capacity and charging and discharging currents are with the spinel-type of the core-shell structure of surface Fe2O3 doping The Mass Calculation of nickel ion doped.
The cycle performance of battery charge and discharge under 2C multiplying power in embodiment 2 is as follows: battery is by 100 circle circulations, battery Capacity basically no attenuation, remains at 115mAh/g or so, coulombic efficiency substantially 100%, have good capacity retention ratio, Service life and coulombic efficiency.
Embodiment 3
1, the nuclear-shell structure type nickel ion doped of surface zinc doping is prepared
By spinel-type nickel ion doped LiNi in flask0.5Mn1.5O4-δThe presoma of (0≤δ < 0.1) powder 0.5g, zinc Acetic acid dihydrate zinc 15.0mg, precipitating reagent sodium bicarbonate 2g are dispersed in 30ml water, obtain reaction system.In the reaction system In, the concentration of the spinel-type nickel ion doped is 16.7g/L；The acetic acid dihydrate zinc concentration is 2.2 × 10-3mol/L； The concentration of the sodium bicarbonate is 0.79mol/L.
Regulator acetic acid is added into reaction system to adjust pH to 5.5, is stirred 4 hours at 90 DEG C, be centrifuged, washed It washs, be dried to obtain intermediate product.
Intermediate product is warming up to 800 DEG C again with 10 DEG C/min of rate, calcines 4 hours at this temperature, obtains surface The spinel-type nickel ion doped powder of the core-shell structure of zinc doping.Its kernel is spinel nickel LiMn2O4 LiNi0.5Mn1.5O4-δ(0 ≤ δ < 0.1), the zinc doping amount of shell is the 0.89wt% of spinel nickel LiMn2O4.The thickness of shell is about 10nm.
2, the electrode of the spinel-type nickel ion doped of the core-shell structure of surface zinc doping is prepared
By the spinel-type nickel ion doped powder 0.24g of the core-shell structure of the surface zinc doping of above-mentioned preparation and conductive addition Agent super-p 0.03g, binder PVDF 0.03g and a little solvent NMP mixing, through slurrying, smear, (aluminium foil is as afflux Body), it is dry, obtain the spinel-type nickel ion doped electrode of the core-shell structure of surface zinc doping.
3, assembled battery
It is anode with the spinel-type nickel ion doped electrode of the core-shell structure of surface zinc doping obtained in above-mentioned steps 2, It is assembled into battery with cathode of lithium, electrolyte selects concentration for the carbonic ester electrolyte of 1M, wherein solvent are as follows: DMC:DEC:EC= 1:1:1 (W/W), solute are 1.0M LiPF6。
4, battery testing
Constant current charge-discharge test is carried out to above-mentioned battery using storage battery charge/discharge tester, test voltage section is 3.0 ~5.0V, test temperature are 25 DEG C.Battery capacity and charging and discharging currents are with the spinel-type of the core-shell structure of surface zinc doping The Mass Calculation of nickel ion doped.
The cycle performance of battery charge and discharge under 2C multiplying power in embodiment 3 is as follows: battery is by 100 circle circulations, battery Capacity basically no attenuation, remains at 114mAh/g or so, coulombic efficiency substantially 100%, have good capacity retention ratio, Service life and coulombic efficiency.
Embodiment 4
1, the titanium doped nuclear-shell structure type nickel ion doped in preparation surface
By spinel-type nickel ion doped LiNi in flask0.5Mn1.5O4-δThe presoma of (0≤δ < 0.1) powder 0.5g, titanium Butyl titanate 20mg, precipitating reagent urea 2g are dispersed in 30ml ethyl alcohol, obtain reaction system.In the reaction system, institute The concentration for stating spinel-type nickel ion doped is 16.7g/L；The concentration of the butyl titanate is 2.0 × 10-3mol/L；The urine The concentration of element is 1.11mol/L.
The regulator hydrochloric acid (1mol/L) that 1ml is added into reaction system adjusts pH value to 5, stirs 4 hours at 90 DEG C, Through centrifugation, washs, is dried to obtain intermediate product.
Intermediate product is warming up to 800 DEG C again with 15 DEG C/min of rate and is calcined 4 hours at this temperature, table is obtained The spinel-type nickel ion doped powder of the titanium doped core-shell structure in face.Its kernel is spinel nickel LiMn2O4 LiNi0.5Mn1.5O4-δ (0≤δ < 0.1), the Fe2O3 doping amount of shell are the 0.56wt% of spinel nickel LiMn2O4.The thickness of shell is about 15nm.
2, the electrode of the spinel-type nickel ion doped of the titanium doped core-shell structure in preparation surface
By the spinel-type nickel ion doped powder 0.24g of the titanium doped core-shell structure in the surface of above-mentioned preparation and conductive addition Agent super-p 0.03g, binder PVDF 0.03g and a little solvent NMP mixing, through slurrying, smear, (aluminium foil is as afflux Body), it is dry, obtain the spinel-type nickel ion doped electrode of the titanium doped core-shell structure in surface.
3, assembled battery
It is anode with the spinel-type nickel ion doped electrode of the titanium doped core-shell structure in above-mentioned surface, is assembled into cathode of lithium Battery, electrolyte select concentration for the carbonic ester electrolyte of 1M, wherein solvent are as follows: DMC:DEC:EC=1:1:1 (W/W), solute For 1.0M LiPF6.
4, battery testing
Constant current charge-discharge test is carried out to above-mentioned battery using storage battery charge/discharge tester, test voltage section is 3.0 ~5.0V, test temperature are 25 DEG C.Battery capacity and charging and discharging currents are with the spinel-type of the titanium doped core-shell structure in surface The Mass Calculation of nickel ion doped.
The cycle performance of battery charge and discharge under 2C multiplying power in embodiment 3 is as follows: battery is by 100 circle circulations, battery Capacity basically no attenuation, remains at 114mAh/g or so, coulombic efficiency substantially 100%, have good capacity retention ratio, Service life and coulombic efficiency.

Claims (29)

1. a kind of positive electrode, which is characterized in that the positive electrode is spinel-type nickel ion doped LiNi0.5Mn1.5O4-δ, 0≤ δ < 0.1, have in the spinel-type nickel ion doped inwardly adulterate from surface ground concentration gradually decrease metallic element, thus Doped layer close and close-connected with inner core, also referred to as shell are formd, the thickness of the shell is greater than 0, the metal The doping of element accounts for percentage composition x≤10wt% of the spinel-type nickel ion doped weight.
2. positive electrode according to claim 1, which is characterized in that 0 < x≤5wt%.
3. positive electrode according to claim 2, which is characterized in that 0 < x≤2wt%.
4. positive electrode according to claim 3, which is characterized in that 0.29≤x≤0.89wt%.
5. positive electrode according to claim 4, which is characterized in that 0.56≤x≤0.62wt%.
6. positive electrode according to any one of claims 1-5, which is characterized in that the shell with a thickness of 1~ 50nm。
7. positive electrode according to claim 6, which is characterized in that the shell with a thickness of 1~50nm.
8. positive electrode according to claim 7, which is characterized in that the shell with a thickness of 1~30nm.
9. positive electrode according to claim 8, which is characterized in that the shell with a thickness of 10~25nm.
10. positive electrode according to claim 9, which is characterized in that the shell with a thickness of 15nm or 20nm.
11. positive electrode according to any one of claims 1-5, which is characterized in that the metallic element be selected from Mg, One of Ca, Al, Ti, Fe, Co, Cu, Zn, Zr or a variety of.
12. a kind of method for preparing positive electrode described in any one of claim 1-11, which is characterized in that the method includes Following steps:
(1) by raw material spinel-type nickel ion doped LiNi0.5Mn1.5O4-δ, 0≤δ < 0.1, the presoma and precipitating of doping metals In a solvent, regulator is added to adjust the pH value of reaction system to 1.5~7.0, heating stirring is reacted, so that introducing in agent dispersion The presoma be converted into the solid-phase compound containing the doped metallic elements, and uniform deposition is in the spinel-type nickel manganese The surface of sour lithium, separates after the reaction was completed, washs, dry, obtains intermediate product；
(2) intermediate product is ground uniformly, calcining is cooled to room temperature, obtains the positive electrode；
In step (1), the reaction is precipitating-heat leak reaction of metal ion.
13. preparation method according to claim 12, which is characterized in that in step (1), the solvent is water or ethyl alcohol.
14. preparation method according to claim 12, which is characterized in that in step (1), the precipitating reagent be carbonate, One of bicarbonate, formates, acetate, hydrophosphate and phosphate are a variety of.
15. preparation method according to claim 12, which is characterized in that in step (1), the presoma is selected from metal member At least one of chlorate, sulfate, nitrate, perchlorate, acetate and the alkoxide of element.
16. preparation method according to claim 15, which is characterized in that the metallic element be Mg, Ca, Al, Ti, Fe, One of Co, Cu, Zn, Zr or a variety of.
17. preparation method according to claim 16, which is characterized in that the presoma is ANN aluminium nitrate nonahydrate, six water Close one of iron chloride, acetic acid dihydrate zinc or butyl titanate or a variety of.
18. preparation method described in any one of 2-17 according to claim 1, which is characterized in that the precipitating reagent is selected from carbonic acid Hydrogen ammonium, ammonium carbonate, sodium bicarbonate, sodium carbonate, saleratus, potassium carbonate, ammonium formate, ammonium acetate, formamide, acetamide, urea, Diammonium hydrogen phosphate, ammonium dihydrogen phosphate, triammonium phosphate, disodium-hydrogen, sodium dihydrogen phosphate, sodium phosphate, potassium phosphate,monobasic, di(2-ethylhexyl)phosphate One of hydrogen potassium and potassium phosphate are a variety of.
19. preparation method according to claim 18, which is characterized in that the precipitating reagent is diammonium hydrogen phosphate and ammonium formate Mixture, ammonium formate, sodium bicarbonate or urea.
20. preparation method according to claim 12, which is characterized in that in step (1), it is described to adjust that regulator is added The pH value of reaction system is to 2.0~5.5.
21. preparation method according to claim 12, which is characterized in that the temperature that is stirred to react in the step (1) is 20~95 DEG C, the reaction time is 2~4 hours.
22. preparation method according to claim 12, which is characterized in that in the step (2), with 1~50 DEG C of heating Rate is warming up to 200~1200 DEG C and calcines 1~10 hour.
23. preparation method according to claim 22, which is characterized in that in the step (2), with 1~50 DEG C of heating Rate is warming up to 450~800 DEG C, calcines 3~4 hours.
24. preparation method according to claim 12, which is characterized in that in the reaction system of step (1), the former material The concentration for expecting spinel nickel LiMn2O4 is 0.01g/L~1000g/L；The concentration of the presoma is 1 × 10-6Mol/L~ 0.1mol/L；The concentration of the precipitating reagent is 1 × 10-6Mol/L~10mol/L.
25. preparation method according to claim 24, which is characterized in that in the reaction system of step (1), the former material The concentration for expecting spinel nickel LiMn2O4 is 0.1g/L~100g/L, and the concentration of the presoma is 1 × 10-5Mol/L~ 0.01mol/L；The concentration of the precipitating reagent is 1 × 10-5Mol/L~1mol/L.
26. preparation method according to claim 25, which is characterized in that in the reaction system of step (1), the former material The concentration for expecting spinel nickel LiMn2O4 is 1g/L~80g/L, and the concentration of the presoma is 1 × 10-4Mol/L~1 × 10- 3mol/L。
27. preparation method according to claim 26, which is characterized in that in the reaction system of step (1), the former material The concentration for expecting spinel nickel LiMn2O4 is 20~50g/L.
28. a kind of electrode comprising positive electrode of any of claims 1-11.
29. a kind of battery comprising electrode described in claim 28.
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