CN102983323A - Positive pole material of lithium ion secondary battery and preparation method of material - Google Patents
Positive pole material of lithium ion secondary battery and preparation method of material Download PDFInfo
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Abstract
The invention provides a positive pole material of a lithium ion secondary battery. The positive pole material of the lithium ion secondary battery is represented by using a general formula of Li1+xNiyCozMn1-x-y-zO2, wherein x is more than or equal to 0 and is less than or equal to 0.3, y is more than or equal to 0 and is less than or equal to 0.3 and z is more than or equal to 0 and is less than or equal to 0.3. The invention further comprises a preparation method of the positive pole material, a positive pole of the lithium ion secondary battery using the positive pole material, and the lithium ion secondary battery. With the adoption of the preparation method provided by the invention, the lithium enrichment layer-like solid solution positive pole material with ordered surface and internal height of crystalline grains can be obtained only through lithium excess and simple treatment of water treatment; and the lithium enrichment layer-like solid solution positive pole material for the lithium ion secondary battery, which has the characteristics of good crystallization degree, high purity, good rate discharge property and circular property, can be conveniently and rapidly prepared.
Description
Technical field
The invention belongs to the battery technology field, be specifically related to a kind of lithium ion secondary battery anode material and preparation method thereof, lithium ion secondary battery positive electrode and lithium rechargeable battery.
Background technology
Secondary cell is called again rechargeable battery, is can make active material activate the battery that continues use by the mode of charging behind battery discharge.With respect to dry cell, the cycle charging number of times of secondary cell can reach thousands of to tens thousand of times, is a kind of novel environment-friendly battery.
Secondary cell in the market mainly comprises lead-acid battery, ickel-cadmium cell, Ni-MH battery and lithium ion battery.The comparatively environmental protection but energy density is lower of lead-acid battery low price but contain the heavy metal lead of contaminated environment, ickel-cadmium cell, the Ni-MH battery energy density is higher but have slight memory effect, and efficiency for charge-discharge is poor under the hot environment.With respect to lead-acid battery, ickel-cadmium cell and Ni-MH battery, lithium ion battery has higher specific energy, the discharge curve balance, and self-discharge rate is low, and cycle life is longer, memory-less effect, environmentally safe is the green battery that grew up in the last few years.
Lithium rechargeable battery comprises positive pole, negative pole, is arranged on barrier film and electrolyte between positive pole and the negative pole.Wherein, positive pole comprises matrix and the coating material that is coated on this matrix, and wherein coating material comprises positive electrode (positive active material), electric conducting material and binding agent.Positive electrode is the crucial raw material of lithium rechargeable battery, because positive electrode occupies larger weight ratio in lithium rechargeable battery, so the positive electrode performance has determined build, fail safe and the electric property of battery.
Along with quick consumption and the incident serious greenhouse effect of the fossil fuels 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 the clean energy resource field, and it is good to have a fail safe, and the characteristics such as good cycle has extended cycle life, and is nontoxic are hopeful to be used as large-sized power power supply and large-scale accumulation power supply.Because cobalt acid lithium price is high, security performance is relatively poor, can't be used for the large-scale power supply of this class; Although spinel lithium manganate is safe, cheap, its energy density is low, and cycle performance and high-temperature behavior are poor, and the manganese dissolution problems was outstanding when carbon was made negative pole; Phosphate system has that cost is low, high security and the good advantages such as cycle performance, but also exist energy density on the low side, the electron conduction of material body is poor, the comparatively complicated series of problems that waits of preparation technology, material quality is further improved, and positive electrode that therefore must development of new satisfies the needs of large-scale lithium ion battery.Nearest a kind of high power capacity solid-solution material has been subject to paying close attention to widely, and its main component is manganese nickel cobalt, and wherein the content of manganese accounts for more than the 50wt%, therefore price is much lower with respect to the sour lithium price of cobalt, and in addition, it is large that this material also has energy density, therefore the power density high receives much concern.One of its subject matter 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 its application in high-capacity lithium-ion power battery and lithium ion storage battery.As the means of improving, people have attempted that fluoride coating, oxide coat and carbon coats to improve the cyclicity of solid-solution material.Because thereby these coating layers mostly are the reversible capacity that the material of non-electrochemical activity has reduced material, and these process of surface treatment also can increase the cost of material.In addition, also there is report to improve the cycle characteristics of material by the method (step-by-step treatment) that progressively activates rich lithium material, yet this method belongs to formation process in the battery fabrication, the very long processing time is all unfavorable for shipment and the cost of battery, does not also have basic help for improving multiplying power property.
The cycle characteristics of rich lithium layed solid-solution material and multiplying power property is relatively poor with its crystal structure close relationship.In general, the Li that comprises the electrochemistry inertia in the rich lithium layed solid-solution material
2MnO
3Two parts of Li-Ni-Co-O with electro-chemical activity.Distribution owing to its microcosmic of reason of preparation condition between two kinds is very different.Restricted impact for condition, the inside of material grains and surface often have a large amount of defectives and exist, and the existence of these defectives is the basic factors that affect its circulation and multiplying power property.
Summary of the invention
In view of this, the object of the present invention is to provide orderly rich lithium layed solid-solution lithium ion secondary battery anode material of a kind of surface and crystal grain internal height and preparation method thereof.
For achieving the above object, the invention provides following technical scheme:
Lithium ion secondary battery anode material of the present invention is used general formula Li
1+xNi
yCo
zMn
1-x-y-zO
2Expression, wherein 0≤x≤0.3,0≤y≤0.3,0≤z≤0.3.
The present invention also provides a kind of method for preparing above-mentioned lithium ion secondary battery anode material, specifically comprises the steps:
With Li
1+xNi
yCo
zMn
1-x-y-zO
2The water-soluble Li source compound of proportioning weighing, water-soluble nickel source compound, aqueous cobalt source compound and water-soluble manganese source compound, 0≤x≤0.3 wherein, 0≤y≤0.3,0≤z≤0.3, water-soluble Li source compound is excessive, add deionized water mixing wiring solution-forming, the described solution of spray drying obtains mixture, with described mixture 700 ~ 1000 ℃ of lower quick preheatings in air atmosphere, then 700 ~ 1000 ℃ of calcining 6 ~ 20h in Muffle furnace after the cooling, grind naturally, the deionized water washing is repeatedly dried.
Described water-soluble Li source compound is selected from lithium acetate, lithium nitrate, lithium hydroxide or lithium carbonate; Described water-soluble nickel source compound is selected from nickel acetate, nickel nitrate, nickel chloride or nickelous sulfate; Described aqueous cobalt source compound is selected from cobalt acetate, cobalt nitrate, cobalt chloride or cobaltous sulfate; Described water-soluble manganese source compound is selected from manganese acetate, manganese nitrate, manganese chloride or manganese sulfate.
Preferably, described water-soluble Li source compound is lithium hydroxide; Described water-soluble nickel source compound is nickel acetate; Described aqueous cobalt source compound is cobalt acetate; Described water-soluble manganese source compound is manganese acetate.
Further, the invention provides a kind of lithium ion secondary battery positive electrode, comprise matrix and the coating material that places matrix surface, described coating material comprises: above-mentioned positive electrode, electric conducting material and bonding agent.
Further, the present invention also provides a kind of lithium rechargeable battery, comprising: above-mentioned lithium ion secondary battery positive electrode, negative pole, be arranged on barrier film and electrolyte between positive pole and the negative pole.
The present invention obtains surface and the orderly rich lithium layed solid-solution positive electrode of crystal grain internal height, and then obtains easily and fast high-quality, high performance rich lithium layed solid-solution positive electrode by the control of the condition in the sample building-up process.
In sum, by synthetic method and the condition of using among the present invention, can prepare easily and fast have good degree of crystallinity, high purity, excellent multiplying power discharging characteristic and the rich lithium layed solid-solution positive electrode of cycle characteristics.
Description of drawings
In order to be illustrated more clearly in the technical scheme in the embodiment of the invention, the accompanying drawing of required use was done to introduce simply during the below will describe embodiment, apparently, accompanying drawing relevant of the present invention in the following describes only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the X-ray diffractogram of the sample of acquisition among comparative example 1 of the present invention and the embodiment 1 ~ 4;
Fig. 2 is at room temperature low range cycle characteristics figure of the sample that obtains among comparative example 2 of the present invention and the embodiment 5 ~ 6;
Fig. 3 is the cycle characteristics figure of sample under the room temperature different multiplying that obtains among comparative example 3 of the present invention and the embodiment 7 ~ 8;
Fig. 4 is the sample high-resolution-ration transmission electric-lens figure that obtains among comparative example 1 of the present invention and the embodiment 4, and wherein 4a is that comparative example Isosorbide-5-Nitrae b is embodiment 4.
Embodiment
The invention discloses a kind of lithium ion secondary battery anode material, use general formula Li
1+xNi
yCo
zMn
1-x-y-zO
2Expression, wherein 0≤x≤0.3,0≤y≤0.3,0≤z≤0.3.
The present invention also provides a kind of method for preparing above-mentioned lithium ion secondary battery anode material, specifically comprises the steps:
With Li
1+xNi
yCo
zMn
1-x-y-zThe water-soluble Li source compound of proportioning weighing of O2, water-soluble nickel source compound, aqueous cobalt source compound and water-soluble manganese source compound, 0≤x≤0.3 wherein, 0≤y≤0.3,0≤z≤0.3, water-soluble Li source compound is excessive, add deionized water mixing wiring solution-forming, the described solution of spray drying obtains mixture, with described mixture 700 ~ 1000 ℃ of lower quick preheatings in air atmosphere, then 700 ~ 1000 ℃ of calcining 6 ~ 20h in Muffle furnace after the cooling, grind naturally, the deionized water washing is repeatedly dried.
Described water-soluble Li source compound is selected from lithium acetate, lithium nitrate, lithium hydroxide or lithium carbonate; Described water-soluble nickel source compound is selected from nickel acetate, nickel nitrate, nickel chloride or nickelous sulfate; Described aqueous cobalt source compound is selected from cobalt acetate, cobalt nitrate, cobalt chloride or cobaltous sulfate; Described water-soluble manganese source compound is selected from manganese acetate, manganese nitrate, manganese chloride or manganese sulfate.
Among the following embodiment, described water-soluble Li source compound is lithium hydroxide; Described water-soluble nickel source compound is nickel acetate; Described aqueous cobalt source compound is cobalt acetate; Described water-soluble manganese source compound is manganese acetate.
Spray drying is the method that makes the liquid material drying of atomisation in the hothouse thermal current.The powder that mixed solution is carried out obtaining after the spray drying treatment has higher degree, with respect to traditional solution crystal process, spray drying process need not again to product wash, the reprocessing such as dry, the operating process of simplification.And the dry run of spraying drying method is very fast, is suitable for industry and quantizes to produce.The present invention can adopt air-blast atomization seasoning, pressure type atomization drying method or rotation type atomization seasoning, and there is no particular restriction to this in the present invention.
Further, the invention provides a kind of lithium ion secondary battery positive electrode, comprise matrix and the coating material that places matrix surface, described coating material comprises: above-mentioned positive electrode, electric conducting material and bonding agent.
Matrix can adopt material well known to those skilled in the art in the above-mentioned lithium ion secondary battery positive electrode, such as aluminium foil; Electric conducting material is preferably conductive black super P in the coating material; Bonding agent can be polytetrafluoroethylene, polyvinylidene chloride, polyvinyl chloride, polymethyl methacrylate or butadiene-styrene rubber.
Lithium ion secondary battery positive electrode provided by the invention can adopt following method preparation:
Make positive plate on the matrix with being dissolved in 1-METHYLPYRROLIDONE (NMP) and being pressed in after above-mentioned lithium ion secondary battery anode material, electric conducting material, the binding agent mixing.
Further, the present invention also provides a kind of lithium rechargeable battery, comprising: above-mentioned lithium ion secondary battery positive electrode, negative pole, be arranged on barrier film and electrolyte between positive pole and the negative pole.
The present invention does not have particular restriction to described Separator for Lithium-ion battery, considers from cost factor, is preferably polyethylene barrier film or polypropylene diaphragm.
The present invention does not have particular restriction to described electrolyte of lithium-ion secondary battery, can be for well known to a person skilled in the art the nonaqueous electrolytic solution for serondary lithium battery, as contain LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiCH
3SO
3, LiN (SO
2CF
3)
2, LiC (SO
2CF
3)
3, LiAlCl
4, LiSiF
6, LiB (C
6H
5)
4, one or more the electrolytical nonaqueous electrolytic solutions among LiCl and the LiBr, be preferably LiPF
6Nonaqueous electrolytic solution.
The general formula of the present invention's preparation is Li
1+xNi
yCo
zMn
1-x-y-zO
2Lithium ion secondary battery anode material can be used as the positive electrode of column lithium ion battery, rectangular lithium ion battery and button-shaped lithium ion battery, and can be used as the positive electrode of lithium-ion-power cell and lithium-ion energy storage battery.
Below in conjunction with the accompanying drawing in the embodiment of the invention, the technical scheme in the embodiment of the invention is described in detail, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, the every other embodiment that those of ordinary skills obtain under the prerequisite of not making creative work belongs to the scope of protection of the invention.
Comparative example 1
With Li
1.2Ni
0.17Co
0.07Mn
0.56O
2Proportioning weighing lithium hydroxide (5wt% is excessive in the lithium source), nickel acetate, cobalt acetate and manganese acetate, add the solution that deionized water is made into 0.2mol/L after mixing, described solution is obtained mixture with the spray dryer drying, with described mixture in air atmosphere at 850 ℃ of quick preheatings, then 850 ℃ of calcining 14h in Muffle furnace grind oven dry after the cooling.
Embodiment 1
With Li
1.2Ni
0.17Co
0.07Mn
0.56O
2Proportioning weighing lithium hydroxide (7wt% is excessive in the lithium source), nickel acetate, cobalt acetate and manganese acetate, add the solution that deionized water is made into 0.2mol/L after mixing, described solution is obtained mixture with the spray dryer drying, with described mixture in air atmosphere at 700 ℃ of quick preheatings, then 700 ℃ of calcining 20h in Muffle furnace grind oven dry after the cooling.
With Li
1.2Ni
0.17Co
0.07Mn
0.56O
2Proportioning weighing lithium hydroxide (9wt% is excessive in the lithium source), nickel acetate, cobalt acetate and manganese acetate, add the solution that deionized water is made into 0.2mol/L after mixing, described solution is obtained mixture with the spray dryer drying, with described mixture in air atmosphere at 1000 ℃ of quick preheatings, then 1000 ℃ of calcining 6h in Muffle furnace grind oven dry after the cooling.
Embodiment 3
With Li
1.2Ni
0.17Co
0.07Mn
0.56O
2Proportioning weighing lithium hydroxide (10wt% is excessive in the lithium source), nickel acetate, cobalt acetate and manganese acetate, add the solution that deionized water is made into 0.2mol/L after mixing, described solution is obtained mixture with the spray dryer drying, with described mixture in air atmosphere at 800 ℃ of quick preheatings, then 800 ℃ of calcining 12h in Muffle furnace grind oven dry after the cooling.
Embodiment 4
With Li
1.2Ni
0.17Co
0.07Mn
0.56O
2Proportioning weighing lithium hydroxide (10wt% is excessive in the lithium source), nickel acetate, cobalt acetate and manganese acetate, add the solution that deionized water is made into 0.2mol/L after mixing, described solution is obtained mixture with the spray dryer drying, with described mixture in air atmosphere at 800 ℃ of quick preheatings, then in Muffle furnace 800 ℃ the calcining 12h, it is with deionized water washing 2 times, for subsequent use after the oven dry after cooling is ground.
As can be seen from Figure 1, no matter be comparative example 1, or embodiment 1 ~ 4, the sample that the experiment route that designs according to us obtains is not all seen the existence of impurity peaks in their X ray diffracting spectrum, show very high purity.
Comparative example 2
The sample of comparative example 1 preparation is mixed in the 7:2:1 ratio with conductive black super P, binding agent PVDF, be dissolved in the 1-METHYLPYRROLIDONE (NMP), be coated in after stirring and make positive plate on the aluminium foil, described positive plate is descended dry 12h at 120 ℃ in vacuum drying oven, with dried positive plate, assemble in being full of the glove box of high-purity argon gas with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation, obtain CR2016 type button experimental cell.
Charging and discharging currents is 20 milliamperes of every grams, and the charging/discharging voltage interval is between 2 ~ 4.8 volts.Supporting electrolyte is LiPF in the described electrolyte
6, solvent is ethylene carbonate (EC) with diethyl carbonate (DEC) by volume for 1:1 mixes, and the concentration of described electrolyte is 1mol/L, and the battery testing temperature is room temperature.
The sample of embodiment 3 preparations is mixed in the 7:2:1 ratio with conductive black super P, binding agent PVDF, be dissolved in the 1-METHYLPYRROLIDONE (NMP), be coated in after stirring and make positive plate on the aluminium foil, described positive plate is descended dry 12h at 120 ℃ in vacuum drying oven, with dried positive plate, assemble in being full of the glove box of high-purity argon gas with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation, obtain CR2032 type button experimental cell.
Charging and discharging currents is 20 milliamperes of every grams, and the charging/discharging voltage interval is between 2 ~ 4.8 volts.Supporting electrolyte is LiPF in the described electrolyte
6, solvent is ethylene carbonate (EC) with diethyl carbonate (DEC) by volume for 1:1 mixes, and the concentration of described electrolyte is 1mol/L, and the battery testing temperature is room temperature.
Embodiment 6
The sample of embodiment 4 preparations is mixed in the 7:2:1 ratio with conductive black super P, binding agent PVDF, be dissolved in the 1-METHYLPYRROLIDONE (NMP), be coated in after stirring and make positive plate on the aluminium foil, described positive plate is descended dry 12h at 120 ℃ in vacuum drying oven, with dried positive plate, assemble in being full of the glove box of high-purity argon gas with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation, obtain CR2032 type button experimental cell.
Charging and discharging currents is 20 milliamperes of every grams, and the charging/discharging voltage interval is between 2 ~ 4.8 volts.Supporting electrolyte is LiPF in the described electrolyte
6, solvent is ethylene carbonate (EC) with diethyl carbonate (DEC) by volume for 1:1 mixes, and the concentration of described electrolyte is 1mol/L, and the battery testing temperature is room temperature.
As can be seen from Figure 2, by the sample that comparative example 2 obtains, low current discharge (20mA/g) initial discharge specific capacity is the every grams of 290 Milliampere Hours, and capability retention is 91% after the 40 circle circulations.Along with the introducing of excessive lithium, the initial discharge specific capacity of embodiment 5 is reduced to the every gram of 145 Milliampere Hours, and its capacity increases gradually along with circulation, reaches the every gram of 197 Milliampere Hours behind 40 circles.And after the washing processing, the initial capacity of embodiment 6 is the every grams of 264 Milliampere Hours, and still can remain on the every gram of 260 Milliampere Hours after 40 circle circulations, and its special capacity fade is slow, has showed preferably cycle performance.
Comparative example 3
The sample of comparative example 1 preparation is mixed in the 7:2:1 ratio with conductive black super P, binding agent PVDF, be dissolved in the 1-METHYLPYRROLIDONE (NMP), be coated in after stirring and make positive plate on the aluminium foil.Described positive plate is descended dry 12h at 120 ℃ in vacuum drying oven, with dried positive plate, assemble in being full of the glove box of high-purity argon gas with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation, obtain CR2032 type button experimental cell.
Charging current is 20 milliamperes of every grams, and discharging current is respectively 20 milliamperes of every grams, 40 milliamperes of every grams, 100 milliamperes of every grams, 200 milliamperes of every grams and 20 milliamperes of every grams, and the charging/discharging voltage interval is between 2 ~ 4.8 volts.Supporting electrolyte is LiPF in the described electrolyte
6, solvent is ethylene carbonate (EC) with diethyl carbonate (DEC) by volume for 1:1 mixes, and the concentration of described electrolyte is 1mol/L, and the battery testing temperature is room temperature.
Embodiment 7
The sample of embodiment 3 preparations is mixed in the 7:2:1 ratio with conductive black super P, binding agent PVDF, be dissolved in the 1-METHYLPYRROLIDONE (NMP), be coated in after stirring and make positive plate on the aluminium foil, described positive plate is descended dry 12h at 120 ℃ in vacuum drying oven, with dried positive plate, assemble in being full of the glove box of high-purity argon gas with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation, obtain CR2032 type button experimental cell.
Charging current is 20 milliamperes of every grams, and discharging current is respectively 20 milliamperes of every grams, 40 milliamperes of every grams, 100 milliamperes of every grams, 200 milliamperes of every grams and 20 milliamperes of every grams, and the charging/discharging voltage interval is between 2 ~ 4.8 volts.Supporting electrolyte is LiPF in the described electrolyte
6, solvent is ethylene carbonate (EC) with diethyl carbonate (DEC) by volume for 1:1 mixes, and the concentration of described electrolyte is 1mol/L, and the battery testing temperature is room temperature.
Embodiment 8
The sample of embodiment 4 preparations is mixed in the 7:2:1 ratio with conductive black super P, binding agent PVDF, be dissolved in the 1-METHYLPYRROLIDONE (NMP), be coated in after stirring and make positive plate on the aluminium foil, described positive plate is descended dry 12h at 120 ℃ in vacuum drying oven, with dried positive plate, assemble in being full of the glove box of high-purity argon gas with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation, obtain CR2032 type button experimental cell.
Charging current is 20 milliamperes of every grams, and discharging current is respectively 20 milliamperes of every grams, 40 milliamperes of every grams, 100 milliamperes of every grams, 200 milliamperes of every grams and 20 milliamperes of every grams, and the charging/discharging voltage interval is between 2 ~ 4.8 volts.Supporting electrolyte is LiPF in the described electrolyte
6, solvent is ethylene carbonate (EC) with diethyl carbonate (DEC) by volume for 1:1 mixes, and the concentration of described electrolyte is 1mol/L, and the battery testing temperature is room temperature.
As can be seen from Figure 3, by the sample that comparative example 3 obtains, low discharging current (20mA/g) specific capacity is the every grams of 290 Milliampere Hours, but when heavy-current discharge (200mA/g), specific capacity is the every grams of 167 Milliampere Hours, its capacity attenuation or apparent in view.And the sample that obtains by embodiment 7 and embodiment 8, low discharging current (20mA/g) specific capacity is respectively the every gram of 140 Milliampere Hours and the every gram of 276 Milliampere Hours, when when heavy-current discharge (200mA/g), specific capacity is respectively the every gram of 173 Milliampere Hours and the every gram of 201 Milliampere Hours, its special capacity fade is slow, has showed preferably high rate performance.
Fig. 4 is the transmission electron microscope high-resolution comparison mutually of gained sample among gained sample and the embodiment 4 in the comparative example 1, can find out, the material that the technique that proposes among use the present invention and method obtain is the bulk structure high-sequential not only, surface texture also is very orderly, and this is exactly the basic reason that its cycle characteristics and multiplying power property are improved.
Do not need to coat or the complicated technology such as nanometer, the simple process of excessive by lithium in water treatment only, our prepared material has regular internal structure external structure, so its high rate performance is greatly improved.This cost that not only helps to reduce material promotes the suitability for industrialized production of lithium-rich anode material, and the further demand of satisfying the market has also proposed a kind of new approach for the exploitation of rich lithium stratified material.Therefore this system material is a kind of novel high-performance positive electrode.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned example embodiment, and in the situation that does not deviate from spirit of the present invention or essential characteristic, can realize the present invention with other concrete form.Therefore, no matter from which point, all should regard embodiment as exemplary, and be nonrestrictive, scope of the present invention is limited by claims rather than above-mentioned explanation, therefore is intended to include in the present invention dropping on the implication that is equal to important document of claim and all changes in the scope.Any Reference numeral in the claim should be considered as limit related claim.
In addition, be to be understood that, although this specification is described according to execution mode, but be not that each execution mode only comprises an independently technical scheme, this narrating mode of specification only is for clarity sake, those skilled in the art should make specification as a whole, and the technical scheme among each embodiment also can through appropriate combination, form other execution modes that it will be appreciated by those skilled in the art that.
Claims (6)
1. a lithium ion secondary battery anode material is characterized in that: use general formula Li
1+xNi
yCo
zMn
1-x-y-zO
2Expression, wherein 0≤x≤0.3,0≤y≤0.3,0≤z≤0.3.
2. the preparation method of the described lithium ion secondary battery anode material of claim 1 is characterized in that, comprises the steps:
With Li
1+xNi
yCo
zMn
1-x-y-zO
2The water-soluble Li source compound of proportioning weighing, water-soluble nickel source compound, aqueous cobalt source compound and water-soluble manganese source compound, 0≤x≤0.3 wherein, 0≤y≤0.3,0≤z≤0.3, water-soluble Li source compound is excessive, add deionized water mixing wiring solution-forming, the described solution of spray drying obtains mixture, with described mixture 700 ~ 1000 ℃ of lower quick preheatings in air atmosphere, then 700 ~ 1000 ℃ of calcining 6 ~ 20h in Muffle furnace after the cooling, grind naturally, the deionized water washing is repeatedly dried.
3. preparation method according to claim 2, it is characterized in that: described water-soluble Li source compound is selected from lithium acetate, lithium nitrate, lithium hydroxide or lithium carbonate; Described water-soluble nickel source compound is selected from nickel acetate, nickel nitrate, nickel chloride or nickelous sulfate; Described aqueous cobalt source compound is selected from cobalt acetate, cobalt nitrate, cobalt chloride or cobaltous sulfate; Described water-soluble manganese source compound is selected from manganese acetate, manganese nitrate, manganese chloride or manganese sulfate.
4. preparation method according to claim 3, it is characterized in that: described water-soluble Li source compound is lithium hydroxide; Described water-soluble nickel source compound is nickel acetate; Described aqueous cobalt source compound is cobalt acetate; Described water-soluble manganese source compound is manganese acetate.
5. a lithium ion secondary battery positive electrode comprises matrix and the coating material that places matrix surface, and it is characterized in that: described coating material comprises lithium ion secondary battery anode material claimed in claim 1, electric conducting material and bonding agent.
6. a lithium rechargeable battery is characterized in that, comprising: lithium ion secondary battery positive electrode claimed in claim 5, negative pole, be arranged on barrier film and electrolyte between positive pole and the negative pole.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413928A (en) * | 2013-05-20 | 2013-11-27 | 龙能科技（苏州）有限公司 | High-capacity high-compaction metal oxide anode material and preparation method thereof |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101764210A (en) * | 2010-01-14 | 2010-06-30 | 镇江科捷锂电池有限公司 | Anode material of lithium battery in Al2O3 wrapping manganese-base layered crystal structure |
| CN101777643A (en) * | 2010-01-14 | 2010-07-14 | 镇江科捷锂电池有限公司 | Preparation method of anode material of Al2O3-cladding manganese-based laminated lithium battery |
| CN102157733A (en) * | 2011-03-10 | 2011-08-17 | 江苏科捷锂电池有限公司 | Anode material of manganese-based lamellar crystal structure lithium battery and manufacturing method thereof |
| CN102655230A (en) * | 2011-03-03 | 2012-09-05 | 苏州大学 | Cathode material for lithium ion secondary battery, preparation method of cathode material, lithium ion secondary battery anode and lithium ion secondary battery |
-
2012
- 2012-12-19 CN CN201210555365.1A patent/CN102983323B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101764210A (en) * | 2010-01-14 | 2010-06-30 | 镇江科捷锂电池有限公司 | Anode material of lithium battery in Al2O3 wrapping manganese-base layered crystal structure |
| CN101777643A (en) * | 2010-01-14 | 2010-07-14 | 镇江科捷锂电池有限公司 | Preparation method of anode material of Al2O3-cladding manganese-based laminated lithium battery |
| CN102655230A (en) * | 2011-03-03 | 2012-09-05 | 苏州大学 | Cathode material for lithium ion secondary battery, preparation method of cathode material, lithium ion secondary battery anode and lithium ion secondary battery |
| CN102157733A (en) * | 2011-03-10 | 2011-08-17 | 江苏科捷锂电池有限公司 | Anode material of manganese-based lamellar crystal structure lithium battery and manufacturing method thereof |
Non-Patent Citations (6)
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413928A (en) * | 2013-05-20 | 2013-11-27 | 龙能科技（苏州）有限公司 | High-capacity high-compaction metal oxide anode material and preparation method thereof |
| 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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