CN102983323B - Lithium ion secondary battery anode material and preparation method thereof - Google Patents
Lithium ion secondary battery anode material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of lithium ion secondary battery anode material, use formula Li1+xNiyCozMn1‑x‑y‑zO2Represent, wherein 0≤x≤0.3,0≤y≤0.3,0≤z≤0.3；Present invention also offers the preparation method of above-mentioned positive electrode, and use lithium ion secondary battery positive electrode and the lithium rechargeable battery of above-mentioned positive electrode.The simple process that the present invention processes only by lithium excess and water, obtain the lithium-rich solid solution cathode material of surface and intra-die high-sequential, can prepare easily and fast and there is good degree of crystallinity, high purity, excellent rate discharge characteristic and the lithium-rich solid solution lithium ion secondary battery anode material of cycle characteristics.
Description
Technical field
The invention belongs to cell art, be specifically related to a kind of lithium ion secondary battery anode material and
Preparation method, lithium ion secondary battery positive electrode and lithium rechargeable battery.
Background technology
Secondary cell, is also called rechargeable battery, is can to make activity by the way of charging after battery discharge
Substance activating and the battery that is continuing with.Relative to aneroid battery, the cycle charging number of times of secondary cell up to
Thousands of to tens thousand of times, be a kind of novel environment-friendly battery.
Secondary cell in the market mainly include lead-acid battery, ickel-cadmium cell, Ni-MH battery and lithium from
Sub-battery.Lead-acid battery low price but containing pollute environment heavy metal lead, ickel-cadmium cell more environmental protection
But energy density is relatively low, Ni-MH battery energy density is higher but has slight memory effect, hot environment
Lower efficiency for charge-discharge is poor.Relative to lead-acid battery, ickel-cadmium cell and Ni-MH battery, lithium ion battery has
Higher specific energy, discharge curve balances, and self-discharge rate is low, and cycle life is longer, memory-less effect,
Environmentally safe, is the green battery grown up in the last few years.
Lithium rechargeable battery includes positive pole, negative pole, the barrier film being arranged between positive pole and negative pole and electrolysis
Liquid.Wherein, positive pole includes matrix and the coating material being coated on this matrix, and wherein coating material includes
Positive electrode (positive active material), conductive material and binding agent.Positive electrode is lithium rechargeable battery
Key raw material, owing to positive electrode occupies bigger weight ratio in lithium rechargeable battery, therefore
Positive electrode performance determines the build of battery, safety and electric property.
Along with quickly consuming and incident serious greenhouse effect of the Fossil fuel such as oil, coal,
People also grow with each passing day for the demand of the regenerative resource of cleaning.Lithium rechargeable battery belongs to cleaning energy
The features such as source domain, has safety good, and good cycle has extended cycle life, nontoxic, have uncommon
Prestige is used as large-sized power power supply and large-scale accumulation power supply.Owing to cobalt acid lithium price is high, security performance is poor,
It is not used in this kind of large-scale power supply；Although spinel lithium manganate safety is high, cheap, but its
Energy density is low, and cycle performance and high-temperature behavior are poor, and carbon is made manganese problems of dissolution during negative pole and highlighted；Phosphate
System has the advantages such as low cost, high security and good cycle performance, but it is inclined to there is also energy density
Low, the electron conduction of material body is poor, and preparation technology is complex waits series of problems, material quality
It is further improved, it is therefore necessary to novel positive electrode will be developed to meet large-scale lithium ion battery
Need.A kind of high capacity solid solution material is of great interest, and its main component is manganese nickel
Cobalt, wherein the content of manganese accounts for more than 50wt%, and therefore price is much lower relative to cobalt acid lithium price, this
Outward, it is big that this material also has energy density, and therefore power density high receives much concern.It is main
Problem one is that cycle performance has much room for improvement, and another is that its multiplying power property is poor.This will have a strong impact on
It stores the application in battery at high-capacity lithium-ion power battery and lithium ion.As the means improved,
People have attempted fluoride cladding, oxide cladding and carbon cladding and have improved the cyclicity of solid-solution material.
Owing to these clads mostly are the material of non-electroactive thus reduce the reversible capacity of material, and
These process of surface treatment also can increase the cost of material.Additionally, also have been reported that by progressively activating rich lithium
The method (step-by-step treatment) of material improves the cycle characteristics of material, but this method
Belonging to formation process in battery fabrication, the very long time that processes is for the shipment of battery and cost the most not
Profit, does not has basic help for improving multiplying power property yet.
The cycle characteristics of lithium-rich solid-solution material is poor with multiplying power property is to have close with its crystal structure
The relation cut.It is, in general, that lithium-rich solid-solution material comprises the Li of electrochemicaUy inert2MnO3
Two parts of Li-Ni-Co-O with electro-chemical activity.Due to its microcosmic of reason of preparation condition between two kinds
Distribution be very different.Being affected by preparation condition, inside and the surface of material grains often have
Substantial amounts of defect exists, and the existence of these defects is the basic factor affecting its circulation with multiplying power property.
Summary of the invention
In view of this, it is an object of the invention to provide the rich lithium of a kind of surface and intra-die high-sequential
Layed solid-solution lithium ion secondary battery anode material and preparation method thereof.
For achieving the above object, the present invention provides following technical scheme:
The molecular formula of the lithium ion secondary battery anode material of the present invention is: Li1.2Ni0.17Co0.07Mn0.56O2。。
Present invention also offers a kind of method preparing above-mentioned lithium ion secondary battery anode material, specifically wrap
Include following step:
With Li1.2Ni0.17Co0.07Mn0.56O2Proportioning weigh water-soluble lithium source compound, water solublity nickel source
Compound, aqueous cobalt source compound and water solublity manganese source compound, water-soluble lithium source compound excess, add
Deionized water mixing wiring solution-forming, is spray-dried described solution and obtains mixture, by described mixture at sky
Quick preheating at 700～1000 DEG C in gas atmosphere, then 700～1000 DEG C of calcinings 6～20 in Muffle furnace
H, after natural cooling, grinds, and deionized water wash repeatedly, is dried.
Described water-soluble lithium source compound is in lithium acetate, lithium nitrate, Lithium hydrate or lithium carbonate
A kind of；Described water solublity nickel source compound is in nickel acetate, nickel nitrate, Nickel dichloride. or nickel sulfate
A kind of；Described aqueous cobalt source compound is in cobaltous acetate, cobalt nitrate, cobaltous chloride or cobaltous sulfate
A kind of；Described water solublity manganese source compound is in manganese acetate, manganese nitrate, manganese chloride or manganese sulfate
A kind of.
Preferably, described water-soluble lithium source compound is Lithium hydrate；Described water solublity nickel source chemical combination
Thing is nickel acetate；Described aqueous cobalt source compound is cobaltous acetate；Described water solublity manganese source compound
For manganese acetate.
Further, the present invention provides a kind of lithium ion secondary battery positive electrode, including matrix be placed in matrix
The coating material on surface, described coating material includes: above-mentioned positive electrode, conductive material and bonding agent.
Further, the present invention also provides for a kind of lithium rechargeable battery, including: above-mentioned lithium ion secondary
Anode, negative pole, setting barrier film between a positive electrode and a negative electrode and electrolyte.
The present invention is controlled by the condition in sample building-up process, obtains surface and intra-die high-sequential
Lithium-rich solid solution cathode material, and then obtain high-quality, high performance rich lithium layer easily and fast
Shape solid solution cathode material.
In sum, by the synthetic method used in the present invention and condition, can prepare easily and fast
There is good degree of crystallinity, high purity, excellent rate discharge characteristic and the lithium-rich of cycle characteristics
Solid solution cathode material.
Accompanying drawing explanation
For the technical scheme being illustrated more clearly that in the embodiment of the present invention, in embodiment being described below
The required accompanying drawing used is briefly described, it should be apparent that, for the present invention in describing below
Accompanying drawing is only some embodiments of the present invention, for those of ordinary skill in the art, is not paying
On the premise of creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the X-ray diffractogram of the sample obtained in comparative example 1 of the present invention and embodiment 1～4；
Fig. 2 is the sample at room temperature low range circulation obtained in comparative example 2 of the present invention and embodiment 5～6
Performance plot；
Fig. 3 is that the sample obtained in comparative example 3 of the present invention and embodiment 7～8 is under room temperature different multiplying
Cycle characteristics figure；
Fig. 4 is the sample high-resolution-ration transmission electric-lens figure obtained in comparative example 1 of the present invention and embodiment 4, its
Middle 4a be comparative example Isosorbide-5-Nitrae b be embodiment 4.
Detailed description of the invention
The invention discloses a kind of lithium ion secondary battery anode material, use formula
Li1+xNiyCozMn1-x-y-zO2Represent, wherein 0≤x≤0.3,0≤y≤0.3,0≤z≤0.3.
Present invention also offers a kind of method preparing above-mentioned lithium ion secondary battery anode material, specifically wrap
Include following step:
With Li1+xNiyCozMn1-x-y-zO2Proportioning weigh water-soluble lithium source compound, water solublity nickel source chemical combination
Thing, aqueous cobalt source compound and water solublity manganese source compound, wherein 0≤x≤0.3,0≤y≤0.3,0
≤ z≤0.3, water-soluble lithium source compound excess, add deionized water mixing wiring solution-forming, be spray-dried institute
State solution and obtain mixture, by described mixture quick preheating at 700～1000 DEG C in air atmosphere,
Then 700～1000 DEG C of calcinings 6～20h in Muffle furnace, after natural cooling, grind, deionized water wash
Repeatedly, dry.
Described water-soluble lithium source compound is selected from lithium acetate, lithium nitrate, Lithium hydrate or lithium carbonate；Institute
The water solublity nickel source compound stated is selected from nickel acetate, nickel nitrate, Nickel dichloride. or nickel sulfate；Described is water-soluble
Property cobalt source compound selected from cobaltous acetate, cobalt nitrate, cobaltous chloride or cobaltous sulfate；Described water solublity manganese source
Compound is selected from manganese acetate, manganese nitrate, manganese chloride or manganese sulfate.
In following embodiment, described water-soluble lithium source compound is Lithium hydrate；Described water solublity
Nickel source compound is nickel acetate；Described aqueous cobalt source compound is cobaltous acetate；Described water solublity manganese
Source compound is manganese acetate.
Spray drying is the method making the liquid material of atomisation be dried in hothouse thermal current.Will be mixed
Close the powder obtained after solution carries out spray drying treatment and there is higher degree, relative to traditional solution knot
Crystallization, spray drying method is without post processings such as washing product, be dried, the operating process of simplification.
Further, the dry run of spraying drying method is very fast, is suitable for commercial quantities metaplasia and produces.The present invention is permissible
Use air-blast atomization seasoning, pressure type atomization drying method or rotation type atomization seasoning, the present invention couple
There is no particular restriction for this.
Further, the present invention provides a kind of lithium ion secondary battery positive electrode, including matrix be placed in matrix
The coating material on surface, described coating material includes: above-mentioned positive electrode, conductive material and bonding agent.
In above-mentioned lithium ion secondary battery positive electrode, matrix can use material well known to those skilled in the art,
Such as aluminium foil；In coating material, conductive material is preferably conductive black super P；Bonding agent can be polytetrafluoro
Ethylene, polyvinylidene chloride, polrvinyl chloride, polymethyl methacrylate or butadiene-styrene rubber.
The lithium ion secondary battery positive electrode that the present invention provides can be adopted and prepare with the following method:
It is dissolved in N-first after above-mentioned lithium ion secondary battery anode material, conductive material, binding agent mixing
Base ketopyrrolidine (NMP) is also pressed on matrix and makes positive plate.
Further, the present invention also provides for a kind of lithium rechargeable battery, including: above-mentioned lithium ion secondary
Anode, negative pole, setting barrier film between a positive electrode and a negative electrode and electrolyte.
Described Separator for Lithium-ion battery is not particularly limited by the present invention, considers from cost factor,
It is preferably polyethylene diagrams or polypropylene diaphragm.
Described electrolyte of lithium-ion secondary battery is not particularly limited by the present invention, can be art technology
The known nonaqueous electrolytic solution for serondary lithium battery of personnel, as containing LiPF6、LiBF4、LiAsF6、
LiClO4、LiCH3SO3、LiN(SO2CF3)2、LiC(SO2CF3)3、LiAlCl4、LiSiF6、LiB(C6H5)4、
The nonaqueous electrolytic solution of one or more electrolyte in LiCl and LiBr, preferably LiPF6Non-aqueous solution electrolysis
Liquid.
Formula prepared by the present invention is Li1+xNiyCozMn1-x-y-zO2Lithium ion secondary battery anode material can
Using as column lithium ion battery, rectangular lithium ion battery and the positive electrode of button-shaped lithium ion battery,
And can be as lithium-ion-power cell and the positive electrode of lithium-ion energy storage battery.
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out
Detailed description, it is clear that described embodiment is only a part of embodiment of the present invention rather than complete
The embodiment in portion.Based on the embodiment in the present invention, those of ordinary skill in the art are not making creation
Property work on the premise of the every other embodiment that obtained, broadly fall into the scope of protection of the invention.
Comparative example 1
With Li1.2Ni0.17Co0.07Mn0.56O2Proportioning weigh Lithium hydrate (lithium source 5wt% excess), acetic acid
Nickel, cobaltous acetate and manganese acetate, add deionized water and be made into the solution of 0.2mol/L, by described molten after mixing
Liquid spray dryer is dried to obtain mixture, by described mixture in air atmosphere quickly pre-at 850 DEG C
Burning processes, and then 850 DEG C of calcining 14h in Muffle furnace, grind after cooling and dry.
Embodiment 1
With Li1.2Ni0.17Co0.07Mn0.56O2Proportioning weigh Lithium hydrate (lithium source 7wt% excess), acetic acid
Nickel, cobaltous acetate and manganese acetate, add deionized water and be made into the solution of 0.2mol/L, by described molten after mixing
Liquid spray dryer is dried to obtain mixture, by described mixture in air atmosphere quickly pre-at 700 DEG C
Burning processes, and then 700 DEG C of calcining 20h in Muffle furnace, grind after cooling and dry.
Embodiment 2
With Li1.2Ni0.17Co0.07Mn0.56O2Proportioning weigh Lithium hydrate (lithium source 9wt% excess), acetic acid
Nickel, cobaltous acetate and manganese acetate, add deionized water and be made into the solution of 0.2mol/L, by described molten after mixing
Liquid spray dryer is dried to obtain mixture, by described mixture in air atmosphere at 1000 DEG C quickly
Preheating, then 1000 DEG C of calcining 6h in Muffle furnace, grind after cooling and dry.
Embodiment 3
With Li1.2Ni0.17Co0.07Mn0.56O2Proportioning weigh Lithium hydrate (lithium source 10wt% excess), vinegar
Acid nickel, cobaltous acetate and manganese acetate, add deionized water and be made into the solution of 0.2mol/L, by described after mixing
Solution spray dryer is dried to obtain mixture, by described mixture in air atmosphere at 800 DEG C quickly
Preheating, then 800 DEG C of calcining 12h in Muffle furnace, grind after cooling and dry.
Embodiment 4
With Li1.2Ni0.17Co0.07Mn0.56O2Proportioning weigh Lithium hydrate (lithium source 10wt% excess), vinegar
Acid nickel, cobaltous acetate and manganese acetate, add deionized water and be made into the solution of 0.2mol/L, by described after mixing
Solution spray dryer is dried to obtain mixture, by described mixture in air atmosphere at 800 DEG C quickly
Preheating, then 800 DEG C of calcining 12h in Muffle furnace, cooling is washed with deionized 2 after grinding
Secondary, standby after drying.
From figure 1 it appears that either comparative example 1, or embodiment 1～4, according to our design
The sample that experiment route obtains, does not the most see impurity peaks in their X ray diffracting spectrum,
Show the highest purity.
Comparative example 2
The sample prepared by comparative example 1 is mixed in 7:2:1 ratio with conductive black super P, binding agent PVDF
Close, be dissolved in N-Methyl pyrrolidone (NMP), be coated in after stirring on aluminium foil and make positive plate,
Described positive plate is dried in vacuum drying oven at 120 DEG C 12h, by dried positive plate, with metal
Negative pole, polypropylene diaphragm and electrolyte prepared by lithium sheet assembles in the glove box of full high-purity argon gas,
Obtain CR2016 type button experimental cell.
Charging and discharging currents is 20 milliamperes every gram, and charging/discharging voltage is interval between 2～4.8 volts.Described electrolysis
In liquid, supporting electrolyte is LiPF6, solvent is that ethylene carbonate (EC) is pressed with diethyl carbonate (DEC)
Volume ratio is that 1:1 mixes, and the concentration of described electrolyte is 1mol/L, and battery testing temperature is room temperature.
Embodiment 5
Sample embodiment 3 prepared is mixed in 7:2:1 ratio with conductive black super P, binding agent PVDF
Close, be dissolved in N-Methyl pyrrolidone (NMP), be coated in after stirring on aluminium foil and make positive plate,
Described positive plate is dried in vacuum drying oven at 120 DEG C 12h, by dried positive plate, with metal
Negative pole, polypropylene diaphragm and electrolyte prepared by lithium sheet assembles in the glove box of full high-purity argon gas,
Obtain CR2032 type button experimental cell.
Charging and discharging currents is 20 milliamperes every gram, and charging/discharging voltage is interval between 2～4.8 volts.Described electrolysis
In liquid, supporting electrolyte is LiPF6, solvent is that ethylene carbonate (EC) is pressed with diethyl carbonate (DEC)
Volume ratio is that 1:1 mixes, and the concentration of described electrolyte is 1mol/L, and battery testing temperature is room temperature.
Embodiment 6
Sample embodiment 4 prepared is mixed in 7:2:1 ratio with conductive black super P, binding agent PVDF
Close, be dissolved in N-Methyl pyrrolidone (NMP), be coated in after stirring on aluminium foil and make positive plate,
Described positive plate is dried in vacuum drying oven at 120 DEG C 12h, by dried positive plate, with metal
Negative pole, polypropylene diaphragm and electrolyte prepared by lithium sheet assembles in the glove box of full high-purity argon gas,
Obtain CR2032 type button experimental cell.
Charging and discharging currents is 20 milliamperes every gram, and charging/discharging voltage is interval between 2～4.8 volts.Described electrolysis
In liquid, supporting electrolyte is LiPF6, solvent is that ethylene carbonate (EC) is pressed with diethyl carbonate (DEC)
Volume ratio is that 1:1 mixes, and the concentration of described electrolyte is 1mol/L, and battery testing temperature is room temperature.
Figure it is seen that the sample obtained by comparative example 2, low current electric discharge (20mA/g) is just
Beginning specific discharge capacity is 290 Milliampere Hour every gram, and after 40 circle circulations, capability retention is 91%.Along with mistake
The introducing of amount lithium, the initial discharge specific capacity of embodiment 5 is reduced to 145 Milliampere Hour every gram, its capacity
It is gradually increased along with circulation, after 40 circles, reaches 197 Milliampere Hour every gram.And after washing process, implement
The initial capacity of example 6 is 264 Milliampere Hour every gram, and remains to be maintained at 260 millis after 40 circle circulations
Ampere-hour every gram, its special capacity fade is slow, is demonstrated by preferable cycle performance.
Comparative example 3
The sample prepared by comparative example 1 is mixed in 7:2:1 ratio with conductive black super P, binding agent PVDF
Close, be dissolved in N-Methyl pyrrolidone (NMP), be coated in after stirring on aluminium foil and make positive plate.
Described positive plate is dried in vacuum drying oven at 120 DEG C 12h, by dried positive plate, with metal
Negative pole, polypropylene diaphragm and electrolyte prepared by lithium sheet assembles in the glove box of full high-purity argon gas,
Obtain CR2032 type button experimental cell.
Charging current is 20 milliamperes every gram, discharge current be respectively 20 milliamperes every gram, 40 milliamperes every gram,
100 milliamperes every gram, 200 milliamperes every gram and 20 milliamperes every gram, charging/discharging voltage is interval between 2～4.8 volts.
In described electrolyte, supporting electrolyte is LiPF6, solvent is ethylene carbonate (EC) and diethyl carbonate
(DEC) mixing for 1:1 by volume, the concentration of described electrolyte is 1mol/L, battery testing
Temperature is room temperature.
Embodiment 7
Sample embodiment 3 prepared is mixed in 7:2:1 ratio with conductive black super P, binding agent PVDF
Close, be dissolved in N-Methyl pyrrolidone (NMP), be coated in after stirring on aluminium foil and make positive plate,
Described positive plate is dried in vacuum drying oven at 120 DEG C 12h, by dried positive plate, with metal
Negative pole, polypropylene diaphragm and electrolyte prepared by lithium sheet assembles in the glove box of full high-purity argon gas,
Obtain CR2032 type button experimental cell.
Charging current is 20 milliamperes every gram, discharge current be respectively 20 milliamperes every gram, 40 milliamperes every gram,
100 milliamperes every gram, 200 milliamperes every gram and 20 milliamperes every gram, charging/discharging voltage is interval between 2～4.8 volts.
In described electrolyte, supporting electrolyte is LiPF6, solvent is ethylene carbonate (EC) and diethyl carbonate
(DEC) mixing for 1:1 by volume, the concentration of described electrolyte is 1mol/L, battery testing
Temperature is room temperature.
Embodiment 8
Sample embodiment 4 prepared is mixed in 7:2:1 ratio with conductive black super P, binding agent PVDF
Close, be dissolved in N-Methyl pyrrolidone (NMP), be coated in after stirring on aluminium foil and make positive plate,
Described positive plate is dried in vacuum drying oven at 120 DEG C 12h, by dried positive plate, with metal
Negative pole, polypropylene diaphragm and electrolyte prepared by lithium sheet assembles in the glove box of full high-purity argon gas,
Obtain CR2032 type button experimental cell.
Charging current is 20 milliamperes every gram, discharge current be respectively 20 milliamperes every gram, 40 milliamperes every gram,
100 milliamperes every gram, 200 milliamperes every gram and 20 milliamperes every gram, charging/discharging voltage is interval between 2～4.8 volts.
In described electrolyte, supporting electrolyte is LiPF6, solvent is ethylene carbonate (EC) and diethyl carbonate
(DEC) mixing for 1:1 by volume, the concentration of described electrolyte is 1mol/L, battery testing
Temperature is room temperature.
From figure 3, it can be seen that the sample obtained by comparative example 3, low discharging current (20mA/g) compares
Capacity is 290 Milliampere Hour every gram, but when heavy-current discharge (200mA/g), specific capacity is 167
Milliampere Hour every gram, its capacity attenuation or obvious.And obtained by embodiment 7 and embodiment 8
The sample obtained, low discharging current (20mA/g) specific capacity is respectively 140 Milliampere Hours every gram and 276 millis
Ampere-hour every gram, when at heavy-current discharge (200mA/g), it is every that specific capacity is respectively 173 Milliampere Hours
Gram and 201 Milliampere Hours every gram, its special capacity fade is slow, is demonstrated by preferable high rate performance.
Fig. 4 is the transmission electron microscope high-resolution phase of gained sample in gained sample and embodiment 4 in comparative example 1
Comparison, it can be seen that use the material not only body that the technique proposed in the present invention and method are obtained
Phase structure high-sequential, surface texture is also very well ordered, and this is exactly its cycle characteristics and multiplying power spy
Property improve basic reason.
Need not the complicated technologies such as cladding or nanorize, the simple place processed only by lithium excess and water
Reason, our obtained material has regular internal structure external structure, and therefore its high rate performance has obtained greatly
Improvement.It is not only does this facilitate the industrialized production of the cost promotion lithium-rich anode material reducing material, enters
One step meets the demand in market, and the exploitation for lithium-rich material it is also proposed a kind of new approach.Cause
This this system material is a kind of novel high-performance positive electrode.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment,
And without departing from the spirit or essential characteristics of the present invention, it is possible to real in other specific forms
The existing present invention.Therefore, no matter from the point of view of which point, embodiment all should be regarded as exemplary, and
Being nonrestrictive, the scope of the present invention is limited by claims rather than described above, therefore purport
All changes in falling in the implication of equivalency and scope of claim are included in the present invention.
Should not be considered as limiting involved claim by any reference in claim.
Moreover, it will be appreciated that although this specification is been described by according to embodiment, but the most each reality
Mode of executing only comprises an independent technical scheme, and this narrating mode of description is only for understand
Seeing, those skilled in the art should be using description as an entirety, and the technical scheme in each embodiment is also
Other embodiments that it will be appreciated by those skilled in the art that can be formed through appropriately combined.
Claims (3)
1. one kind
The preparation method of lithium ion secondary battery anode material, it is characterised in that comprise the steps:
With Li1.2Ni0.17Co0.07Mn0.56O2Proportioning weigh water-soluble lithium source compound, water solublity nickel source compound, aqueous cobalt source compound, water solublity manganese source compound, water-soluble lithium source compound excess, add deionized water mixing wiring solution-forming, it is spray-dried described solution and obtains mixture, by quick preheating, the then 700～1000 DEG C of calcinings 6～20h in Muffle furnace at 700～1000 DEG C in air atmosphere of described mixture, after natural cooling, grinding, deionized water wash repeatedly, is dried.
Preparation method the most according to claim 1, it is characterised in that: described water-soluble lithium source compound one in lithium acetate, lithium nitrate, Lithium hydrate or lithium carbonate；Described water solublity nickel source compound one in nickel acetate, nickel nitrate, Nickel dichloride. or nickel sulfate；Described aqueous cobalt source compound one in cobaltous acetate, cobalt nitrate, cobaltous chloride or cobaltous sulfate；Described water solublity manganese source compound one in manganese acetate, manganese nitrate, manganese chloride or manganese sulfate.
Preparation method the most according to claim 2, it is characterised in that: described water-soluble lithium source compound is Lithium hydrate；Described water solublity nickel source compound is nickel acetate；Described aqueous cobalt source compound is cobaltous acetate；Described water solublity manganese source compound is manganese acetate.
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| CN104037403A (en) * | 2014-06-24 | 2014-09-10 | 陈海辉 | Method for prolonging service life and improving high-temperature performance of manganese-series lithium ion batteries |
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