CN106887583A - 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 PDFInfo
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- CN106887583A CN106887583A CN201510937404.8A CN201510937404A CN106887583A CN 106887583 A CN106887583 A CN 106887583A CN 201510937404 A CN201510937404 A CN 201510937404A CN 106887583 A CN106887583 A CN 106887583A
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- H01M4/00—Electrodes
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- 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
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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
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Abstract
The invention discloses a kind of positive electrode and its preparation method and application, it is spinel-type nickel ion doped LiNi0.5Mn1.5O4-δ(0≤δ ＜ 0.1), it has the metallic element gradually reduced from the inside doping concentration in surface, so as to form close with inner core and tight shell of the connection thickness more than 0, the doping of metallic element accounts for the 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, recycling heat treatment makes metallic element internally be permeated from nickel ion doped surface, shell is formed in kernel nickel ion doped surface in situ, shell is very high with the structural similarity of kernel, compatibility is good, and perfection solves the problems, such as that nucleocapsid is peeled off.The presence of shell significantly improves the stability of heat endurance, cyclical stability and material self structure of the positive electrode in charge and discharge process, has practicality application prospect very high in energy storage field.
Description
Technical field
The invention belongs to lithium ion battery material technical field, in particular to a kind of positive electrode and its
Preparation method and application.
Background technology
Used as a kind of reliable, efficient energy storage device, lithium ion battery since the advent of the world just establishes its nothing
The status that can shake.Wherein, positive electrode as lithium ion battery core, be always scientific research personnel concern
Emphasis.Conventional positive electrode, is limited to its relatively low energy density and price higher, its table at present
User now can not be still allowed to be satisfied with.Thus, the research and development of high-energy-density positive electrode, with extremely important existing
Sincere justice.
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 normal
Cobalt acid lithium, LiMn2O4 and LiFePO4.Three-dimensional lithium ion diffusion admittance present in spinel structure,
The high power performance of material is effectively ensured, its preparation process is simple has been considered further that, raw material is cheap and easy to get, can
To think that nickel ion doped is a kind of power battery anode material for quite having an application prospect.
Unmodified nickel ion doped material is difficult to the defect that overcomes in the presence of some.Such as in charge and discharge process, by
Higher in nickel ion doped operating voltage, electrode surface can occur side reaction with electrolyte, consume Li+, cause to have
Effect lithium is reduced, and capacity attenuation is serious.In addition, often there is Mn in nickel ion doped crystal3+, material surface
Mn3+Easily disproportionation generation Mn2+And dissolve in the electrolytic solution, cause material surface to be destroyed, ultimately cause
Material capacity decays.
Research shows, by one layer of shell of stabilization of nickel ion doped surface introducing, can effectively suppress material
The side reaction on surface, improves the structural stability of material.At present, the most common mode for constructing stabilization shell
It is exactly coating modification.Wherein, the material such as zinc oxide, aluminum oxide, aluminum fluoride is most commonly seen covering.
But, the lithium ionic mobility and electronic conductivity of these materials are often bad, and the high rate performance of material is often
Can become negatively affected.And, the shell constructed by the method for coating, because shell is complete with inner core
It is complete different, due to Volume Changes when discharge and recharge, easily there is the phenomenon peeled off.It is then desired to seek
More rational means are looked for construct core shell structure.
The content of the invention
The present invention is intended to provide a kind of positive electrode and its preparation method and application, the method deposition process is controllable,
And can form one layer in the surface in situ of kernel spinel-type nickel ion doped has metallic element to adulterate and determination thickness
Finishing coat (also referred to as doped layer or shell), so as to obtain a kind of spinelle of new core shell structure
Type nickel lithium manganate cathode material, the presence of the shell can significantly improve heat of the material in charge and discharge process surely
The stability of qualitative, cyclical stability and material self structure.
To achieve these goals, the invention provides a kind of positive electrode, the positive electrode is spinel-type
Nickel ion doped LiNi0.5Mn1.5O4-δ(0≤δ ＜ 0.1), in the spinel-type nickel ion doped have from surface to
Interior doping ground concentration gradually reduces ground metallic element, close with inner core and close-connected so as to form
Doped layer, also referred to as shell, the thickness of the shell are more than 0, and the doping of the metallic element accounts for spinel-type
Percentage composition x≤the 10wt% of 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%.
Further, the thickness of shell is 1~50nm；Preferably 1~30nm；More preferably 10~25nm,
For example can be 15nm or 20nm.
Further, the metallic element is selected from Mg, Ca, Al, Ti, Fe, Co, Cu, Zn, Zr
In one or more.
Present invention also offers a kind of method 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), doping metals
Presoma and precipitating reagent dispersion in a solvent, add conditioning agent with adjust the pH value of reaction system to
1.5~7.0, heating stirring reaction so that the presoma of introducing is converted into and contains the doped metallic elements
Solid-phase compound, and uniform deposition is on the surface of the spinel-type nickel ion doped, is separated after the completion of reaction,
Washing, dries, and obtains intermediate product；
(2) intermediate product grinding is uniform, calcining is cooled to room temperature, obtains the positive electrode.
Further, reaction described in step (1) is the precipitation-heat leak reaction of metal ion；It is described molten
Agent is water or ethanol.
Further, precipitating reagent described in step (1) be carbonate, bicarbonate, formates, acetate,
One or more in hydrophosphate and phosphate.Further, precipitating reagent be selected from ammonium hydrogen carbonate, ammonium carbonate,
Sodium acid carbonate, 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, phosphoric acid
One or more in sodium, potassium phosphate,monobasic, potassium dihydrogen phosphate and potassium phosphate；More preferably phosphoric acid hydrogen
The mixture of two ammoniums and ammonium formate, ammonium formate, sodium acid carbonate or urea.
Further, presoma described in step (1) is selected from chlorate, sulfate, the nitric acid of metallic element
At least one in salt, perchlorate, acetate and alkoxide；It is preferred that the metallic element can for Mg,
One or more in Ca, Al, Ti, Fe, Co, Cu, Zn, Zr；The presoma for example can be
ANN aluminium nitrate nonahydrate, one or more in ferric chloride hexahydrate, acetic acid dihydrate zinc or butyl titanate.
Further, conditioning agent is added in step (1) to adjust the pH value of the reaction system to 2.0~5.5；
More preferably 3.0~5.0；Conditioning agent be selected from formic acid, acetic acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, ammoniacal liquor,
One kind in NaOH and potassium hydroxide.
Further, the stirring reaction temperature in step (1) is 20~95 DEG C, preferably 30~80 DEG C；Enter one
Step is preferably 45~90 DEG C；Reaction time is 2~4 hours.Can for example be stirred 2 hours at 45 DEG C；Or
Person stirs 2 hours at 50 DEG C；Or stirred 4 hours at 90 DEG C；Or stirring 4 is small at 90 DEG C
When.
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, more preferably 1g/L~80g/L, more preferably
It is 20~50g/L.The concentration of the presoma is 1 × 10-6Mol/L~0.1mol/L；It is preferred that
1×10-5Mol/L~0.01mol/L；More preferably 1 × 10-4Mol/L~1 × 10-3mol/L.The precipitating reagent
Concentration be 1 × 10-6Mol/L~10mol/L, preferably 1 × 10-5Mol/L~1mol/L.
Further, in step (2), 200~1200 DEG C are warming up to 1~50 DEG C/min of heating rate and are forged
Burn 1~10 hour；Preferably, 450~800 DEG C, calcining 3~4 are warming up to 3~15 DEG C/min of heating rate
Hour.
Invention further provides a kind of electrode, it includes above-mentioned positive electrode.
Invention further provides a kind of battery, it includes above-mentioned electrode.
Beneficial effects of the present invention：
The present invention makes metallic element heavy in spinel-type nickel ion doped surface basis weight using the method for controlled precipitation
Product, recycles heat treatment metallic element is internally permeated from spinel-type nickel ion doped surface, so
The spinel-type nickel mangaic acid of layer of metal element doping is formed in the surface in situ of kernel spinel-type nickel ion doped
Lithium finishing coat (also referred to as doped layer or shell).The present invention is by spinel-type nickel ion doped positive pole material
Expecting the surface of particle carries out special metallic element modification, so as to obtain possessing a kind of new core shell structure
Spinel-type nickel ion doped electrode material, its kernel be spinel-type nickel ion doped, i.e. LiNi0.5Mn1.5O4-δ
(0≤δ ＜ 0.1), shell is the spinel-type nickel ion doped doped layer of metallic element doping.It is prepared by the present invention
Core shell structure spinel-type nickel ion doped electrode material, because its shell is non-with the structural similarity of kernel
Chang Gao, compatibility is good, so that perfection solves the problems, such as that nucleocapsid is peeled off.The presence of the shell can be carried significantly
The stability of heat endurance, cyclical stability and material self structure of the material high in charge and discharge process,
There is practicality application prospect very high in energy storage field.
The preparation side of the spinel-type nickel ion doped electrode material for possessing new type structure of hud that the present invention is provided
Method, has been effectively combined cladding in the prior art and the advantage of both modification modes of adulterating, and is a kind of stabilization
Effective surface doping method.Specifically, the method can be on the premise of material overall performance not be influenceed
Passivating material surface, hence it is evident that reduce surface corrosion and surface side reaction, it is possible to efficiently solve shell with
The problem that kernel is peeled off in cyclic process.Meanwhile, surface doping method of the invention has been prepared by height
The spinel-type nickel ion doped material of the new core shell structure that performance kernel and stabilization shell are constituted, this is right
In the extensive ripe application of nickel ion doped material, with extremely real meaning.
Brief description of the drawings
The transmitted electron of the spinel-type nickel ion doped of the core shell structure that Fig. 1 adulterates for the surfaces of aluminum of embodiment 1
Microphotograph；
The EDS of the spinel-type nickel ion doped of the core shell structure that Fig. 2 adulterates for the surfaces of aluminum of embodiment 1 is surveyed
Test result；
The spherical aberration correction of the spinel-type nickel ion doped of the core shell structure that Fig. 3 adulterates for the surfaces of aluminum of embodiment 1
Electron micrograph；And
The spinel-type nickel ion doped of the core shell structure that Fig. 4 adulterates for the surfaces of aluminum of embodiment 1 is in 2C multiplying powers
The cycle performance of lower discharge and recharge.
Specific embodiment
As described above, the invention provides a kind of positive electrode, it is spinel-type nickel ion doped
LiNi0.5Mn1.5O4-δ(0≤δ ＜ 0.1), has in the spinel-type nickel ion doped and inwardly adulterates ground from surface
Concentration gradually reduces ground metallic element, so as to form close with inner core and close-connected doped layer,
Also referred to as shell, the thickness of the shell is more than 0, and the doping of the metallic element accounts for the spinel-type nickel manganese
Percentage composition x≤the 10wt% of sour lithium 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 is by spinel-type nickel ion doped LiNi0.5Mn1.5O4-δThe surface doping of (0≤δ ＜ 0.1) is special
Fixed metallic element, has obtained the doped layer (i.e. shell) with passivated surface, hence it is evident that reduce surface rotten
Erosion and the generation of surface side reaction, and due to being to form shell, thus shell in the surface in situ of kernel
Structure it is highly similar to inner core, efficiently solve what shell and kernel were peeled off during circulating battery
Problem, has obtained by high-performance kernel and has stablized the spinel-type nickel of the new core shell structure that shell is constituted
Lithium manganate material.
According to the present invention, the thickness of shell is 1~50nm；Preferably 1~30nm；More preferably 10~25nm.
For example can also be 15nm or 20nm.The present invention can in the preparation process by controlling doping metals before
The parameters such as the sedimentation time and subsequent calcination temperature and time of body are driven to control the thickness of shell.
Present invention also offers a kind of preparation method of above-mentioned positive electrode, comprise 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 are dispersed in solvent (solvent can be water or ethanol)；Conditioning agent is added afterwards
To adjust the pH value of reaction system to 1.5~7.0, heating stirring is reacted so that the presoma of introducing turns
The solid-phase compound containing the doped metallic elements, and uniform deposition are turned in the spinel-type nickel ion doped
Surface, after the completion of reaction separate, washing, dry, obtain intermediate product.
(2) the intermediate product grinding of step (1) is uniform, calcining is cooled to room temperature, obtains the present invention
Positive electrode.
It is described golden containing the doping for the ease of realizing using the precursor form of the doped metallic elements
The solid-phase compound for belonging to element carries out quantitative, uniform deposition on the surface of kernel spinel-type nickel ion doped.Institute
State chlorate, sulfate, nitrate, perchlorate, acetate and alkoxide that presoma is selected from metallic element
In at least one.It is preferred that metallic element can be Mg, Ca, Al, Ti, Fe, Co, Cu, Zn, Zr
In one or more.Such as presoma can be ANN aluminium nitrate nonahydrate, ferric chloride hexahydrate, two hydration second
One or more in sour zinc or butyl titanate etc..
According to the present invention, in step (1), the pH value of reaction system is adjusted to 1.5~7.0, mainly consider
If too low to pH, it is possible to larger injury is caused to material, therefore the pH of initial reaction system is adjusted to
Suitable scope.
According to the present invention, in step (1), after adjusting the pH value of reaction system, reaction system is heated
And stirring brings it about reaction.Preferably, stirring reaction temperature is 20~95 DEG C；More preferably 30~80 DEG C；
More preferably 45~90 DEG C.The reaction time is 2~4 hours.2 for example can be stirred at 45 DEG C
Hour；Or stirred 2 hours at 50 DEG C；Or stirred 4 hours at 90 DEG C.By heating stirring
Reaction causes that the presoma for introducing is converted into the solid-phase compound containing the doped metallic elements and uniformly sinks
Product is on the surface of spinel-type nickel ion doped.Separated after the completion of question response, washed, dried, in obtaining
Between product.
According to the present invention, in the reaction system of step (1), the concentration of raw material spinel-type nickel ion doped
It is 0.01g/L~1000g/L, preferably 0.1g/L~100g/L, more preferably 1g/L~80g/L, more preferably
It is 20~50g/L.If the concentration of raw material is too high, deposition can be caused too fast, be likely to result in intermediate product conjunction
Into failure.If the concentration of raw material is too low, the product that primary first-order equation can be caused to synthesize 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~0.01
mol/L；More preferably 1 × 10-4Mol/L~1 × 10-3mol/L.If the excessive concentration of presoma, meeting
Cause doping too high, influence the performance of positive electrode；If the concentration of presoma is too low, centre can be caused
Product is difficult to be formed, influence doping 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, metallic element can be caused to deposit too fast, caused
Doping is uneven；If conversely, the concentration of precipitating reagent is too low, metallic element deposition can be caused too low, so that
Cause the doping of metallic element in positive electrode too low, can equally influence the performance of positive electrode.
According to the present invention, in step (2), after the intermediate product grinding uniformly that will be obtained in step (1)
Heat up calcining, and being preferably warming up to 200~1200 DEG C with 1~50 DEG C/min of heating rate calcines 1~10 hour.
450~800 DEG C more preferably are warming up to 3~15 DEG C/min of heating rate, are calcined 3~4 hours.In view of forging
The length of the height and calcination time that burn temperature influences whether the success rate and doping depth of doping, therefore,
Through considering, the present invention preferably will heat up speed, calcining heat and time control in above-mentioned scope.
Invention further provides a kind of electrode, it includes above-mentioned positive electrode.
Invention further provides a kind of battery, it includes above-mentioned electrode.
Below in conjunction with drawings and Examples, the present invention is described in further detail.But those skilled in the art
Understand, protection scope of the present invention is not limited only to following examples.According to present disclosure, ability
Field technique personnel will be recognized that in the situation for not departing from technical characteristic and scope given by technical solution of the present invention
Under, many is made to embodiment described above change and modifications and belong to protection scope of the present invention.
Embodiment 1
1st, the nuclear-shell structure type nickel ion doped of surfaces of aluminum doping is prepared
By spinel-type nickel ion doped LiNi in flask0.5Mn1.5O4-δ(0≤δ ＜ 0.1) powder 0.5g, aluminium
Presoma ANN aluminium nitrate nonahydrate 20mg, precipitating reagent diammonium hydrogen phosphate 10mg, precipitating reagent ammonium formate 2g are dispersed in
In 30ml water, reaction system is obtained.In the reaction system, the concentration of the spinel-type nickel ion doped
It is 16.7g/L；The concentration of the ANN aluminium nitrate nonahydrate is 1.8 × 10-3mol/L；The concentration of the diammonium hydrogen phosphate
It is 2.5 × 10-3Mol/L, the concentration of the ammonium formate is 1.06mol/L.
To conditioning agent hydrochloric acid is added in reaction system to adjust the pH to 3 of the reaction system, at 45 DEG C
Stirring reaction 2 hours, through being centrifuged, washing, be dried to obtain intermediate product.
Intermediate product is warming up to 800 DEG C with 4 DEG C/min of speed, at this temperature calcining 3 hours, afterwards
Room temperature is cooled to, the spinel-type nickel ion doped powder of the core shell structure of surfaces of aluminum doping is obtained.Its kernel is
Spinel-type nickel ion doped LiNi0.5Mn1.5O4-δ(0≤δ ＜ 0.1), the doping of the aluminium in shell is spinelle
The 0.29wt.% of type nickel ion doped.
Fig. 1 be embodiment 1 in obtain surfaces of aluminum doping core shell structure spinel-type nickel ion doped it is saturating
Penetrate electron micrograph, it can be seen that the surface change without exception of nickel ion doped.Nucleocapsid prepared by this explanation
The kernel of the spinel-type nickel lithium manganate cathode material of structure is good with the compatibility of shell, does not have excessive structure
Difference, i.e. structure height are similar.
The spinel-type nickel ion doped of the core shell structure that Fig. 2 adulterates for the surfaces of aluminum obtained in embodiment 1
EDS test results.It can be seen that the concentration that Al elements inwardly adulterate from surface is gradually reduced, doping Al's
The thickness of shell is about 10nm.
The ball of the spinel-type nickel ion doped of the core shell structure that Fig. 3 adulterates for the surfaces of aluminum obtained in embodiment 1
Difference correcting electronic microphotograph.It can be seen that surface doped region (round frame) is arranged with kernel (square frame) atom
Cloth is different, and this explanation forms doped layer (also referred to as shell) in material surface.
2nd, the electrode of the spinel-type nickel ion doped of the core shell structure of surfaces of aluminum doping is prepared
The spinel-type nickel ion doped powder 0.24g of the core shell structure of the surfaces of aluminum doping of above-mentioned preparation is taken, and is led
Electric additive super-p (being provided by Hefei company of Ke Jing Materials Technology Ltd.) 0.03g, binding agent PVDF
(Kynoar) 0.03g and a little solvent NMP (1-METHYLPYRROLIDONE) mix, through slurrying,
Smear (aluminium foil is used as collector), drying, obtain the spinel-type nickel manganese of the core shell structure of surfaces of aluminum doping
Sour lithium electrode.
3rd, assembled battery
The spinel-type nickel ion doped electrode of the core shell structure adulterated with the surfaces of aluminum obtained in above-mentioned steps 2 is made
It is positive pole, battery is assembled into cathode of lithium, electrolyte selection concentration is the carbonic ester electrolyte of 1M, wherein,
Solvent is：DMC (dimethyl carbonate):DEC (diethyl carbonate):EC (ethylene carbonate)=1:1:
1 (W/W), solute is 1.0M LiPF6。
4th, battery testing
Constant current charge-discharge test is carried out to above-mentioned battery using storage battery charge/discharge tester, test voltage is interval
It is 3.0~5.0V, test temperature is 25 DEG C.The nucleocapsid that battery capacity and charging and discharging currents are adulterated with surfaces of aluminum
The Mass Calculation of the spinel-type nickel ion doped of structure.
Fig. 4 is the cycle performance of battery discharge and recharge under 2C multiplying powers of this material.Battery is circulated by 100 circles,
Battery capacity is substantially undamped, remains at 115mAh/g or so, and coulombic efficiency has substantially 100%
Good capability retention, life-span and coulombic efficiency.
Embodiment 2
1st, 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-δ(0≤δ ＜ 0.1) powder 0.5g, iron
Presoma ferric chloride hexahydrate 15mg, precipitating reagent ammonium formate 2g be dispersed in 30ml water, reacted
System.In the reaction system, the concentration of the spinel-type nickel ion doped is 16.7g/L；Six water
The concentration for closing iron chloride is 1.9 × 10-3mol/L；The concentration of the ammonium formate is 1.06mol/L.
To conditioning agent nitric acid is added in reaction system to adjust the pH to 2.0 of the reaction system, at 50 DEG C
Stirring 2 hours, through being centrifuged, washing, be dried to obtain intermediate product.
Intermediate product is warming up to 800 DEG C with 3 DEG C/min of speed, is calcined 3 hours at this temperature, obtained
The spinel-type nickel ion doped powder of the core shell structure of surface Fe2O3 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.
2nd, 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 with lead
Electric additive super-p 0.03g, binding agent PVDF (Kynoar) 0.03g and a little solvent NMP
Mixing, through slurrying, smear (aluminium foil is used as collector), dries, and obtains the core shell structure of surface Fe2O3 doping
Spinel-type nickel ion doped electrode.
3rd, assembled battery
Made with the spinel-type nickel ion doped electrode of the core shell structure of the surface Fe2O3 doping obtained in above-mentioned steps 2
It is positive pole, battery is assembled into cathode of lithium, electrolyte selection concentration is the carbonic ester electrolyte of 1M, wherein,
Solvent is：DMC:DEC:EC=1:1:1 (W/W), solute is 1.0M LiPF6。
4th, battery testing
Constant current charge-discharge test is carried out to above-mentioned battery using storage battery charge/discharge tester, test voltage is interval
It is 3.0~5.0V, test temperature is 25 DEG C.Battery capacity and charging and discharging currents are with the nucleocapsid of surface Fe2O3 doping
The Mass Calculation of the spinel-type nickel ion doped of structure.
The cycle performance of the battery discharge and recharge under 2C multiplying powers in embodiment 2 is as follows：Battery is followed by 100 circles
Ring, battery capacity is substantially undamped, remains at 115mAh/g or so, coulombic efficiency substantially 100%,
With good capability retention, life-span and coulombic efficiency.
Embodiment 3
1st, 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-δ(0≤δ ＜ 0.1) powder 0.5g, zinc
Presoma acetic acid dihydrate zinc 15.0mg, precipitating reagent sodium acid carbonate 2g are dispersed in 30ml water, obtain anti-
Answer system.In the reaction system, the concentration of the spinel-type nickel ion doped is 16.7g/L；Described two
Acetate hydrate zinc concentration is 2.2 × 10-3mol/L；The concentration of the sodium acid carbonate is 0.79mol/L.
To adding conditioning agent acetic acid to adjust pH to 5.5 in reaction system, stirred 4 hours at 90 DEG C,
Through being centrifuged, washing, be dried to obtain intermediate product.
Intermediate product is warming up to 800 DEG C with 10 DEG C/min of speed again, is calcined 4 hours at this temperature,
Obtain the spinel-type nickel ion doped powder of the core shell structure of surface zinc doping.Its kernel is spinel nickel mangaic acid
Lithium 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.
2nd, 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 with lead
Electric additive super-p 0.03g, binding agent PVDF 0.03g and a little solvent NMP mix, through slurrying,
Smear (aluminium foil is used as collector), drying, obtain the spinel-type nickel manganese of the core shell structure of surface zinc doping
Sour lithium electrode.
3rd, assembled battery
Spinel-type nickel ion doped electrode with the core shell structure of the surface zinc doping obtained in above-mentioned steps 2 is
Positive pole, battery is assembled into cathode of lithium, and electrolyte selection concentration is the carbonic ester electrolyte of 1M, wherein,
Solvent is：DMC:DEC:EC=1:1:1 (W/W), solute is 1.0M LiPF6。
4th, battery testing
Constant current charge-discharge test is carried out to above-mentioned battery using storage battery charge/discharge tester, test voltage is interval
It is 3.0~5.0V, test temperature is 25 DEG C.Battery capacity and charging and discharging currents are with the core of surface zinc doping
The Mass Calculation of the spinel-type nickel ion doped of shell structure.
The cycle performance of the battery discharge and recharge under 2C multiplying powers in embodiment 3 is as follows：Battery is followed by 100 circles
Ring, battery capacity is substantially undamped, remains at 114mAh/g or so, coulombic efficiency substantially 100%,
With good capability retention, life-span and coulombic efficiency.
Embodiment 4
1st, the titanium doped nuclear-shell structure type nickel ion doped in surface is prepared
By spinel-type nickel ion doped LiNi in flask0.5Mn1.5O4-δ(0≤δ ＜ 0.1) powder 0.5g, titanium
Presoma butyl titanate 20mg, precipitating reagent urea 2g are dispersed in 30ml ethanol, obtain reaction system.
In the reaction system, the concentration of the spinel-type nickel ion doped is 16.7g/L；The butyl titanate
Concentration be 2.0 × 10-3mol/L；The concentration of the urea is 1.11mol/L.
To adding the conditioning agent hydrochloric acid (1mol/L) of 1ml to adjust pH value to 5 in reaction system, at 90 DEG C
Lower stirring 4 hours, through being centrifuged, washing, be dried to obtain intermediate product.
Intermediate product is warming up to 800 DEG C with 15 DEG C/min of speed again and is calcined 4 hours at this temperature,
Obtain the spinel-type nickel ion doped powder of the titanium doped core shell structure in surface.Its kernel is spinel nickel mangaic acid
Lithium LiNi0.5Mn1.5O4-δ(0≤δ ＜ 0.1), the Fe2O3 doping amount of shell is the 0.56wt% of spinel nickel LiMn2O4.
The thickness of shell is about 15nm.
2nd, the electrode of the spinel-type nickel ion doped of the titanium doped core shell structure in surface is prepared
By the spinel-type nickel ion doped powder 0.24g of the titanium doped core shell structure in the surface of above-mentioned preparation with lead
Electric additive super-p 0.03g, binding agent PVDF 0.03g and a little solvent NMP mix, through slurrying,
Smear (aluminium foil is used as collector), drying, obtain the spinel-type nickel manganese of the titanium doped core shell structure in surface
Sour lithium electrode.
3rd, assembled battery
Spinel-type nickel ion doped electrode with the titanium doped core shell structure in above-mentioned surface as positive pole, with cathode of lithium
Battery is assembled into, electrolyte selection concentration is the carbonic ester electrolyte of 1M, wherein, solvent is：DMC:
DEC:EC=1:1:1 (W/W), solute is 1.0M LiPF6.
4th, battery testing
Constant current charge-discharge test is carried out to above-mentioned battery using storage battery charge/discharge tester, test voltage is interval
It is 3.0~5.0V, test temperature is 25 DEG C.Battery capacity and charging and discharging currents are with nucleocapsid that surface is titanium doped
The Mass Calculation of the spinel-type nickel ion doped of structure.
The cycle performance of the battery discharge and recharge under 2C multiplying powers in embodiment 3 is as follows：Battery is followed by 100 circles
Ring, battery capacity is substantially undamped, remains at 114mAh/g or so, coulombic efficiency substantially 100%,
With good capability retention, life-span and coulombic efficiency.
Claims (10)
1. a kind of positive electrode, it is characterised in that the positive electrode is spinel-type nickel ion doped
LiNi0.5Mn1.5O4-δ(0≤δ ＜ 0.1), has in the spinel-type nickel ion doped and inwardly adulterates ground from surface
Concentration gradually reduces ground metallic element, so as to form close with inner core and close-connected doped layer,
Also referred to as shell, the thickness of the shell is more than 0, and the doping of the metallic element accounts for the spinel-type nickel manganese
Percentage composition x≤the 10wt% of sour lithium 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%.
2. positive electrode according to claim 1, it is characterised in that the thickness of the shell is
1~50nm；Preferably 1~30nm；More preferably 10~25nm, for example, can be 15nm or 20nm.
Preferably, the metallic element is selected from Mg, Ca, Al, Ti, Fe, Co, Cu, Zn, Zr
One or more.
3. a kind of method for preparing positive electrode described in claim 1 or 2, it is characterised in that the side
Method is comprised 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 dispersion in a solvent, add conditioning agent with adjust the pH value of reaction system to
1.5~7.0, heating stirring reaction so that the presoma of introducing is converted into and contains the doped metallic elements
Solid-phase compound, and uniform deposition is on the surface of the spinel-type nickel ion doped, is separated after the completion of reaction,
Washing, dries, and obtains intermediate product；
(2) intermediate product grinding is uniform, calcining is cooled to room temperature, obtains the positive electrode.
In step (1), the reaction is the precipitation-heat leak reaction of metal ion.
In step (1), the solvent is water or ethanol.
In step (1), the precipitating reagent is carbonate, bicarbonate, formates, acetate, phosphoric acid hydrogen
One or more in salt and phosphate.
In step (1), the presoma is selected from chlorate, sulfate, nitrate, the chlorine high of metallic element
At least one in hydrochlorate, acetate and alkoxide；It is preferred that the metallic element can for Mg, Ca, Al,
One or more in Ti, Fe, Co, Cu, Zn, Zr；The presoma for example can be nine hydration nitre
Sour aluminium, one or more in ferric chloride hexahydrate, acetic acid dihydrate zinc or butyl titanate.
4. method according to claim 3, it is characterised in that in the step (2), with 1~50 DEG C/
The heating rate of minute is warming up to 200~1200 DEG C and calcines 1~10 hour；
Preferably, 450~800 DEG C are warming up to 3~15 DEG C/min of heating rate, are calcined 3~4 hours.
5. the preparation method according to claim 3 or 4, it is characterised in that
The precipitating reagent is selected from ammonium hydrogen carbonate, ammonium carbonate, sodium acid carbonate, sodium carbonate, saleratus, carbonic acid
Potassium, ammonium formate, ammonium acetate, formamide, acetamide, urea, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorus
Sour three ammoniums, disodium-hydrogen, sodium dihydrogen phosphate, sodium phosphate, potassium phosphate,monobasic, potassium dihydrogen phosphate and phosphoric acid
One or more in potassium；More preferably mixture, ammonium formate, the carbon of diammonium hydrogen phosphate and ammonium formate
Sour hydrogen sodium or urea.
6. the preparation method according to claim any one of 3-5, it is characterised in that
In step (1), add conditioning agent to adjust the pH value of the reaction system to 2.0~5.5；More preferably
It is 3.0~5.0；
Preferably, the conditioning agent be selected from formic acid, acetic acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, ammoniacal liquor,
One kind in NaOH and potassium hydroxide.
7. the preparation method according to any one of claim 3-6, it is characterised in that
Stirring reaction temperature in the step (1) is 20~95 DEG C, preferably 30~80 DEG C；Further preferably
It is 45~90 DEG C；Reaction time is 2~4 hours；
Can for example be stirred 2 hours at 45 DEG C；Or stirred 2 hours at 50 DEG C；Or at 90 DEG C
Lower stirring 4 hours；Or stirred 4 hours at 90 DEG C.
Alternatively, in the step (2), 200~1200 DEG C of calcinings are warming up to 1~50 DEG C of heating rate
1~10 hour；It is preferred that being warming up to 450~800 DEG C, calcine 3~4 hours.
8. the preparation method according to any one of claim 3-7, it is characterised in that in step (1)
Reaction system in, the concentration of the raw material spinel nickel LiMn2O4 is 0.01g/L~1000g/L, preferably
0.1g/L~100g/L, more preferably 1g/L~80g/L, more preferably 20~50g/L；
The concentration of the presoma is 1 × 10-6Mol/L~0.1mol/L；It is preferred that 1 × 10-5Mol/L~0.01mol/L；
More 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.
9. a kind of electrode, it includes the positive electrode described in claim 1 or 2.
10. a kind of battery, it includes the electrode described in claim 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104766960A (en) * | 2015-04-13 | 2015-07-08 | 河北工业大学 | Method for modifying lithium nickel manganese oxide positive electrode material for lithium ion battery |
| WO2015149211A1 (en) * | 2014-03-31 | 2015-10-08 | Showa Denko K.K. | A positive electrode active material and a li secondary battery |
| CN105118988A (en) * | 2015-10-08 | 2015-12-02 | 清华大学深圳研究生院 | High-voltage spinel-structured cathode material for lithium ion battery as well as preparation method |
| US20150349333A1 (en) * | 2014-05-30 | 2015-12-03 | Samsung Electronics Co., Ltd. | Composite cathode active materials, preparation methods thereof, and lithium batteries including the composite cathode active materials |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102005563B (en) * | 2010-10-19 | 2013-05-01 | 合肥国轩高科动力能源有限公司 | Lithium ion battery high-voltage anode material preparation and surface coating method |
| CN102244258B (en) * | 2011-06-16 | 2013-06-05 | 中南大学 | Multiphase Mn (manganese)-base anode material and preparation method thereof |
| CN103022467B (en) * | 2011-09-28 | 2018-01-05 | 北京当升材料科技股份有限公司 | A kind of lithium manganate material of surface treatment and preparation method thereof |
| KR101587854B1 (en) * | 2012-04-18 | 2016-01-25 | 주식회사 엘지화학 | The Method of Preparing Electrodes for Secondary Battery and the Electrodes Prepared by Using the Same |
| CN103094552B (en) * | 2012-10-12 | 2016-08-03 | 合肥国轩高科动力能源有限公司 | A kind of 5V anode material for lithium-ion batteries LiNi0.5-xmn1.5mxo4surface coating method |
| CN103606660A (en) * | 2013-11-06 | 2014-02-26 | 中国科学院化学研究所 | Alumina-coated granules, as well as preparation method and application thereof |
-
2015
- 2015-12-15 CN CN201510937404.8A patent/CN106887583B/en active Active
-
2016
- 2016-03-23 WO PCT/CN2016/077116 patent/WO2017101233A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015149211A1 (en) * | 2014-03-31 | 2015-10-08 | Showa Denko K.K. | A positive electrode active material and a li secondary battery |
| US20150349333A1 (en) * | 2014-05-30 | 2015-12-03 | Samsung Electronics Co., Ltd. | Composite cathode active materials, preparation methods thereof, and lithium batteries including the composite cathode active materials |
| CN104766960A (en) * | 2015-04-13 | 2015-07-08 | 河北工业大学 | Method for modifying lithium nickel manganese oxide positive electrode material for lithium ion battery |
| CN105118988A (en) * | 2015-10-08 | 2015-12-02 | 清华大学深圳研究生院 | High-voltage spinel-structured cathode material for lithium ion battery as well as preparation method |
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