CN104979528A - Core-shell structure positive material based on phase diagram design and design method of core-shell structure positive material - Google Patents

Core-shell structure positive material based on phase diagram design and design method of core-shell structure positive material Download PDF

Info

Publication number
CN104979528A
CN104979528A CN201410137902.XA CN201410137902A CN104979528A CN 104979528 A CN104979528 A CN 104979528A CN 201410137902 A CN201410137902 A CN 201410137902A CN 104979528 A CN104979528 A CN 104979528A
Authority
CN
China
Prior art keywords
equal
ball
ternary
nucleocapsid
lithium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410137902.XA
Other languages
Chinese (zh)
Inventor
张联齐
郭建
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201410137902.XA priority Critical patent/CN104979528A/en
Publication of CN104979528A publication Critical patent/CN104979528A/en
Pending legal-status Critical Current

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a design method of a spherical or sphere-like lithium ion battery material based on Ni-Co-Mn ternary phase diagram analysis. A positive material is designed as follows: a core component is positioned at a high-capacity area (Ni is more than or equal to 0.7 and less than or equal to 1, and Co is more than or equal to 0 and less than or equal to 0.3) of a phase diagram according to the influence of different contents of Ni, Co and Mn to the performances of the positive material, and a shell material is positioned in a high-safety area (Ni is more than or equal to 1/3 and less than or equal to 0.5, and Mn is more than or equal to 1/3 and less than or equal to 0.5), so that the Li[(NinCo(1-m-n)Mnm)b(NicCodMn(1-c-d)a)]O2 material has high safety and compounding performances of a high-capacity material, wherein a is more than or equal to 0, b is less than or equal to 1, a+b is equal to 1, n is more than or equal to 1/3 and less than or equal to 0.5, m is more than or equal to 1/3 and less than or equal to 0.5, d is more than or equal to 0.7 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 0.3, and d+c is less than or equal to 1. A core-shell structure material can show high specific capacity, high circulatory stability and high safety by the complementation of core and shell functions of the core-shell structure. Compared with a homogeneous-phase multielement material, the material disclosed by the invention has the advantages that the large-scale preparation cost is not increased, the repeatability is high, the batch stability is good, the production management is facilitated, and the large-scale commercialization application needs can be met.

Description

A kind of electricity positive electrode of the nucleocapsid structure lithium based on phase G-Design and method for designing thereof
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, particularly utilize the method for phase G-Design nucleocapsid structure ternary material and the preparation method of this positive electrode and presoma thereof.
Background technology
From Sony corporation of Japan in 1991 by since lithium rechargeable battery commercialization, lithium rechargeable battery is extensive use in " 3C " product just.At present, lithium ion secondary battery anode material still based on cobalt acid lithium, but due to cobalt ore few, expensive, and poisonous, therefore need to study other positive electrodes alternatively product.In recent years, due to ternary material Li [NixCoyMn1-x-y] O2 high power capacity, low cost, the extensive concern of researcher is therefore caused.But due to this material, Ni4+ and Co4+ of material surface and NiO and electrolyte occur in the charge state about about 220 DEG C time, release large calorimetric and oxygen, thus make the cycle performance of material reduce and affect its security performance, and the compacted density of material is difficult to suitable with cobalt acid lithium, so seldom realize commercialization at home at present.Large quantity research finds effectively to protect core material at core material Surface coating one deck " thick " shell recently, improve useful life and the security performance of material, but from bibliographical information and related invention patent, also just rest on the compound experiment of single one-tenth branch to the design of Core-shell structure material at present, also do not find a kind of system effective method conveniently can carry out nucleocapsid structure design to a series of ternary material, the high security that can not propose ternary material for existing market, high power capacity and high-pressure solid carry out corresponding structural design, this scientific research at current domestic and international ternary material and production field or a blank.
Summary of the invention
For above-mentioned prior art, the invention provides a kind of method designed for ball-type or class ball-shaped lithium-ion battery material nucleocapsid structure based on nickel-cobalt-manganese ternary Phase Diagram Analysis.By the large component analysis for ternary phase diagrams and nucleocapsid structure ternary materials all at present, we find that nucleocapsid structure ternary material can show clearly on phasor, and its architectural feature also intuitively can be reflected by phasor, in phasor, zones of different material has the function of its uniqueness simultaneously, can form the functional areas that high power capacity district, high security district and high density area etc. are different.Nuclear material is realized and shell material has complementary functions by carrying out nucleocapsid structure design fast and accurately to difference in functionality district material, become a kind of composite functional material being different from the uniqueness of core or shell itself, the requirement to the high power capacity of ternary material, high security, high compacted density on lithium battery market can be met, fill up a blank of current lithium battery production field.
Another object of the present invention is to provide a kind of new type structure of hud ternary material gone out based on nickel-cobalt-manganese ternary Phase Diagram Analysis method design.Its structural formula is characterized as: Li [(Ni nco 1-m-nmn m) b(Ni cco dmn 1-c-d) a] O 2, wherein 0≤a, b≤1 and a+b=1,1/3≤n≤0.5,1/3≤m≤0.5,1>=d>=0.7,0≤c≤0.3 and d+c≤1.Its gross formula is Li (Ni 0.6co 0.2mn 0.2) O 2.Li (the Ni in the high security district in this kind of Material selec-tion ternary phase diagrams nco 1-m-nmn m) bo 2for material is as shell part; Select the high power capacity district Li (Ni in ternary phase diagrams dco cmn 1-c-d) aO 2for material core part, this ternary material overall performance is compared to existing tertiary cathode material, at specific discharge capacity, cyclical stability, thermal stability and fail safe material overall performance compared to existing tertiary cathode material, specific discharge capacity, cyclical stability, thermal stability and security performance all effectively improve.
Another object of the present invention provides the preparation method of above-mentioned nucleocapsid structure ternary material and presoma thereof.
In order to solve the problems of the technologies described above, the technical scheme that the present invention is achieved is:
The method for designing of the ball-type or class ball-shaped lithium-ion battery material nucleocapsid structure that the present invention is based on nickel-cobalt-manganese ternary Phase Diagram Analysis is: with LiNiO 2, LiCoO 2and LiMnO 2for equilateral triangle three summits; And, at LiNiO 2summit place; The content that Ni content is set to 1, Co and Mn is set to 0 respectively; At LiCoO 2summit place: the content that Co content is set to 1, Ni and Mn is set to 0 respectively; At LiMnO 2summit place: the content that Mn content is set to 1, Co and Ni is set to 0; Molecular formula then in equilateral triangle representated by any point is expressed as Li (Ni xco ymn 1-x-y) O 2, wherein, 0≤x, y≤1.
Further, the region of division 1 >=Ni >=0.6,0≤Co≤0.3,0≤Mn≤0.3 is high power capacity district; Division 1/3≤Ni≤0.5,1/3≤Mn≤0.5, region, 0≤Co≤1/3 are high security district; Division 1/2≤Co≤1,0≤Ni≤1/4,0≤Mn≤1/4 are high density area.
And, be Li [Ni by molecular formula xco ymn 1-x-y] O 2, wherein, the material of 0≤x, y≤1 projects in ternary phase diagrams according to the content of nickel cobalt manganese, and represents with O point; Draw one through the line segment AB of this O point, the terminal A of this line segment AB is projected to high security region, the terminal B of this line segment AB is projected to high capacity regions or high-pressure solid region; Using the composition of the coordinate of described terminal A in high security region as shell material, using the composition of the coordinate of described terminal B in high capacity regions or high-pressure solid region as nuclear material; The mol ratio of described shell material and described nuclear material is b: a, and wherein, a is OA line segment length, and b is OB line segment length; Then: based on nickel-cobalt-manganese ternary Phase Diagram Analysis to the molecular formula after the nucleocapsid structure design of this ternary material be: Li [(Ni nco 1-m-nmn m) b(Ni ccodMn 1-c-d) a] O 2, wherein 0≤a, b≤1 and a+b=1; Li (Ni nco 1-m-nmnm) bo 2for the shell structure of this ternary material, wherein, 1/3≤≤ n≤0.5,1/3≤m≤0.5; Li (Ni dcocMn 1-c-d) aO 2for the nuclear structure of this ternary material, according to be divided into different with high-pressure solid sexual function of ternary material high security: when needs high-capacity material performance, 1>=d>=0.6,0≤c≤0.3 and d+c≤1; When needs high-pressure solid material property, 1/2≤c≤1,0≤d≤1/4 and d+c≤1.
The ball-type that the method for designing of the ball-type or class ball-shaped lithium-ion battery material nucleocapsid structure that the present invention is based on nickel-cobalt-manganese ternary Phase Diagram Analysis draws or class spherical nucleocapsid lithium ion battery material, structural formula is characterized as: Li [(Ni nco 1-m-nmn m) b(Ni cco dmn 1-c-d) a] O 2, wherein 0≤a, b≤1 and a+b=1,1/3≤n≤0.5,1/3≤m≤0.5,1>=d>=0.7,0≤c≤0.3 and d+c≤1; And there is following molecular formula composition: Li (Ni 0.6co 0.2mn 0.2) O 2.
In addition, this material is that ball-type or class are spherical under Electronic Speculum.The diameter of described ball-type or class spherical nucleocapsid composite material is 6-50um, and the thickness of shell structure accounts for the 6-40% of ball-type or class spherical nucleocapsid composite material diameter.
The ball-type that the method for designing of the ball-type or class ball-shaped lithium-ion battery material nucleocapsid structure that the present invention is based on nickel-cobalt-manganese ternary Phase Diagram Analysis draws or class spherical nucleocapsid lithium ion battery material presoma, have following molecular formula composition:
[(Ni nCo 1-m-nMn m)b(NicCodMn 1-c-d) a](OH) 2
Wherein, 0≤a, b≤1 and a+b=1,1/3≤n≤0.5,1/3≤m≤0.5,1 >=d >=0.7,0≤c≤0.3 and d+c≤1.
The preparation method of this ball-type or class spherical nucleocapsid lithium ion battery material presoma, concrete steps are as follows:
(1) in reactor, nickel, cobalt and manganese ternary salting liquid A is added with given pace, wherein, mol ratio=c: the d of Ni: Co: Mn: (1-c-d), wherein, d+c≤1; Between 10-12, carry out coprecipitation reaction by aqueous slkali control ph and obtain solidliquid mixture, the molecular formula of precipitated solid is (Ni cco dmn 1-c-d) (OH) 2, thus form the core of presoma;
(2) at the uniform velocity continue to inject nickel, cobalt and manganese ternary solution B with given pace, wherein, mol ratio=n: 1-n-m: the m of Ni: Co: Mn, 1/3≤n≤0.5,1/3≤m≤0.5, form the housing parts of the presoma be coated on outside above-mentioned presoma core thus;
(3) solidliquid mixture after step (2) having been reacted is separated by centrifugal filtration, washs and at 60-200 DEG C, dry 4-10h to neutrality; The precipitated solid gross formula obtained is (Ni 0.6co 0.2mn 0.2) (HO) 2, this precipitated solid is nucleocapsid structure ternary material precursor.
On the one hand, described nickel, cobalt and manganese ternary salting liquid A are identical with total mole specific concentration of described nickel, cobalt and manganese ternary salting liquid B, and the volume ratio that both are injected in reactor is a: b, wherein 0≤a, b≤1 and a+b=1.
A kind of nucleocapsid structure ternary material for anode material for lithium-ion batteries of the present invention, after pulverizing above-mentioned nucleocapsid structure ternary material precursor and lithium source is baking mixed obtains.
Further, by nucleocapsid structure ternary material precursor pulverize after with lithium carbonate in molar ratio 1: 1 ~ 1: 1.2 mix after multistage roasting in Muffle furnace, its sintering temperature 600-1000 DEG C, roasting time 8-30h, after multistage roasting through cooling, broken, sieve to obtain nucleocapsid structure ternary material.
Compared with prior art, the invention has the beneficial effects as follows: the present invention proposes the method for the design nucleocapsid structure ternary material using nickel-cobalt-manganese ternary phasor accurate quick first, high power capacity can be synthesized based on phase G-Design, the lithium ion secondary battery anode material of high stability and high compacted density, the nucleocapsid structure ternary material kernel portion designed according to this configuration is high-capacity material or high density material, sheathing material is generally high security material, this nucleocapsid structure makes the overall chemical property of material significantly improve, the chemical property of material and useful life and security performance is improve under the prerequisite not increasing material cost.Be simultaneously Li (Ni based on this method of phase G-Design ternary material that utilizes by gross formula 0.6co 0.2mn 0.2) O 2carry out nucleocapsid structural design, prepare a kind of new type structure of hud ternary material Li [(Ni nco 1-m-nmn m) b(Ni cco dmn 1-c-d) a] O 2, wherein 0≤a, b≤1 and a+b=1,1/3≤n≤0.5,1/3≤m≤0.5,1>=d>=0.7,0≤c≤0.3 and d+c≤1.This material while ensure that the specific discharge capacity that more former heterogeneous materials is high, due at the Ni being in scarce lithium state 4+and Co 4+material not easily comes in contact with electrolyte and bad reaction occurs and discharges a large amount of gas, substantially the non-reversible deformation of lattice in charge and discharge process can not be occurred in, make this kind of material have good cyclical stability and thermal stability and security performance compared with the same type of material in bibliographical information, reach the unification of high power capacity and high security.Meanwhile, because this process controllability is good, do not need to change high-accuracy property production equipment and namely can carry out nucleocapsid structure ternary material of the present invention on existing, production cost does not increase; And production technology is not owing to existing any complex operations, and therefore material preparation process repeatability is high, lot stability is good, is applicable to large-scale industrial production, can meets the application demand to height ratio capacity material on market.
Accompanying drawing explanation
Fig. 1 is the SEM figure of comparative example 1 and the embodiment of the present invention 2, embodiment 5, embodiment 8;
Fig. 2 is the first charge-discharge curve chart of the embodiment of the present invention 5, embodiment 8, embodiment 9;
Fig. 3 is the cyclic curve figure of comparative example 1 and the embodiment of the present invention 1, embodiment 2, embodiment 3, embodiment 4;
Fig. 4 is the cyclic curve figure of the embodiment of the present invention 5;
Fig. 5 is the cyclic curve figure of the embodiment of the present invention 6, embodiment 7;
Fig. 6 is the cyclic curve figure of the embodiment of the present invention 8;
Fig. 7 is the cyclic curve figure of the embodiment of the present invention 9;
Fig. 8 is the curve of double curvature figure of comparative example 1 and the embodiment of the present invention 2;
Fig. 9 is the DSC curve chart of comparative example 1 and the embodiment of the present invention 2.
Embodiment
The method for designing of the ball-type or class ball-shaped lithium-ion battery material nucleocapsid structure that the present invention is based on nickel-cobalt-manganese ternary Phase Diagram Analysis is, with LiNiO 2, LiCoO 2and LiMnO 2for equilateral triangle three summits; And, at LiNiO 2summit place; The content that Ni content is set to 1, Co and Mn is set to 0 respectively; At LiCoO 2summit place: the content that Co content is set to 1, Ni and Mn is set to 0 respectively; At LiMnO 2summit place: the content that Mn content is set to 1, Co and Ni is set to 0; Molecular formula then in equilateral triangle representated by any point is expressed as Li (Ni xco ymn 1-x-y) O 2, wherein, 0≤x, y≤1.The region of division 1 >=Ni >=0.6,0≤Co≤0.3,0≤Mn≤0.3 is high power capacity district; Division 1/3≤Ni≤0.5,1/3≤Mn≤0.5, region, 0≤Co≤1/3 are high security district; Division 1/2≤Co≤1,0≤Ni≤1/4,0≤Mn≤1/4 are high density area.And, be Li [Ni by molecular formula xco ymn 1-x-y] O 2, wherein, the material of 0≤x, y≤1 projects in ternary phase diagrams according to the content of nickel cobalt manganese, and represents with O point; Draw one through the line segment AB of this O point, the terminal A of this line segment AB is projected to high security region, the terminal B of this line segment AB is projected to high capacity regions or high-pressure solid region; Using the composition of the coordinate of described terminal A in high security region as shell material, using the composition of the coordinate of described terminal B in high capacity regions or high-pressure solid region as nuclear material; The mol ratio of described shell material and described nuclear material is b: a, and wherein, a is OA line segment length, and b is OB line segment length; Then: based on nickel-cobalt-manganese ternary Phase Diagram Analysis to the molecular formula after the nucleocapsid structure design of this ternary material be: Li [(Ni nco 1-m-nmn m) b(Ni ccodMn 1-c-d) a] O 2, wherein 0≤a, b≤1 and a+b=1; Li (Ni nco 1-m-nmnm) bo 2for the shell structure of this ternary material, wherein, 1/3≤≤ n≤0.5,1/3≤m≤0.5; Li (Ni dcocMn 1-c-d) aO 2for the nuclear structure of this ternary material, according to be divided into different with high-pressure solid sexual function of ternary material high security: when needs high-capacity material performance, 1>=d>=0.6,0≤c≤0.3 and d+c≤1; When needs high-pressure solid material property, 1/2≤c≤1,0≤d≤1/4 and d+c≤1.
Carry out the ball-type that designs or class spherical nucleocapsid lithium ion battery material presoma according to above-mentioned method for designing, there is following molecular formula composition: [(Ni nco 1-m-nmn m) b (NicCodMn 1-c-d) a] (OH) 2, wherein, 0≤a, b≤1 and a+b=1,1/3≤n≤0.5,1/3≤m≤0.5,1>=d>=0.7,0≤c≤0.3 and d+c≤1; Its preparation method is as follows:
(1) in reactor, nickel, cobalt and manganese ternary salting liquid A is added with given pace, wherein, mol ratio=c: the d of Ni: Co: Mn: (1-c-d), wherein, d+c≤1; Between 10-12, carry out coprecipitation reaction by aqueous slkali control ph and obtain solidliquid mixture, the molecular formula of precipitated solid is (Ni cco dmn 1-c-d) (OH) 2, thus form the core of presoma;
(2) at the uniform velocity continue to inject nickel, cobalt and manganese ternary solution B with given pace, wherein, mol ratio=n: 1-n-m: the m of Ni: Co: Mn, 1/3≤n≤0.5,1/3≤m≤0.5, form the housing parts of the presoma be coated on outside above-mentioned presoma core thus;
(3) solidliquid mixture after step (2) having been reacted is separated by centrifugal filtration, washs and at 60-200 DEG C, dry 4-10h to neutrality; The precipitated solid gross formula obtained is (Ni 0.6co 0.2mn 0.2) (HO) 2, this precipitated solid is nucleocapsid structure ternary material precursor.
Tell about detailed process of the present invention by the following examples, provide embodiment to be convenience in order to understand, is never restriction the present invention.
Comparative example 1:
With the salting liquid 50L that 16209g nickelous sulfate, 5425g cobaltous sulfate, 3300g manganese sulfate compound concentration are 2M.The solution prepared is injected with the speed of 1.5L/h the reactor that rotating speed is 400rps, inject the NaOH solution of 4M simultaneously, note regulating aqueous slkali flow velocity, keep pH value between 10-11, inject reactor completely to salting liquid, precursor power has reacted.By the solidliquid mixture after having reacted by centrifugation, wash and at 120 DEG C, dry 24h to neutrality.By presoma and the lithium carbonate after drying in molar ratio 1: 1.05 mix after in Muffle furnace 850 DEG C of roasting 16h, the material after roasting obtains homogeneous LiN after fragmentation is sieved 0.6co 0.2mn 0.2o 2ternary material.This material is made 2032 button cells test.
Embodiment 1:
With the salting liquid 23.5L that 11233g nickelous sulfate, 676 cobaltous sulfates, 397g manganese sulfate compound concentration are 2M.The solution prepared is injected with the speed of 1.5L/h the reactor that rotating speed is 400rps, inject the NaOH solution of 4M simultaneously, note regulating aqueous slkali flow velocity, keep pH value between 10-11, reactor is injected completely to salting liquid, continue to be that the salting liquid 26.5L of 2M squeezes into reactor by 4692g nickelous sulfate, 5078g cobaltous sulfate, 2986g manganese sulfate compound concentration, inject reactor completely to salting liquid, precursor power has reacted.By the solidliquid mixture after having reacted by centrifugation, wash and at 120 DEG C, dry 24h to neutrality.By presoma and the lithium carbonate after drying in molar ratio 1: 1.05 mix after in Muffle furnace 850 DEG C of roasting 16h, the material after roasting must homogeneous single-stage nucleocapsid Li [(Ni after fragmentation is sieved 0.9co 0.05mn 0.05) 0.47(Ni 1/3co 1/3mn 1/3) 0.53] O 2.This material is made 2032 button cells test.
Embodiment 2:
With the salting liquid 30L that 12747g nickelous sulfate, 1724g cobaltous sulfate, 1014g manganese sulfate compound concentration are 2M.The solution prepared is injected with the speed of 1.5L/h the reactor that rotating speed is 400rps, inject the NaOH solution of 4M simultaneously, note regulating aqueous slkali flow velocity, keep pH value between 10-11, reactor is injected completely to salting liquid, continue to be that the salting liquid 10L of 2M squeezes into reactor by 3540g nickelous sulfate, 3830g cobaltous sulfate, 2246g manganese sulfate compound concentration, inject reactor completely to salting liquid, precursor power has reacted.By the solidliquid mixture after having reacted by centrifugation, wash and at 120 DEG C, dry 24h to neutrality.By presoma and the lithium carbonate after drying in molar ratio 1: 1.05 mix after in Muffle furnace 850 DEG C of roasting 16h, after roasting, material must homogeneous single-stage nucleocapsid Li [(Ni after fragmentation is sieved 0.8co 0.1mn 0.1) 0.6(Ni 1/3co 1/3mn 1/3) 0.4] O 2.This material is made 2032 button cells test.
Embodiment 3:
With the salting liquid 16.7L that 7082g nickelous sulfate, 958g cobaltous sulfate, 552g manganese sulfate compound concentration are 2M.The solution prepared is injected with the speed of 1.5L/h the reactor that rotating speed is 400rps, inject the NaOH solution of 4M simultaneously, note regulating aqueous slkali flow velocity, keep pH value between 10-11, reactor is injected completely to salting liquid, continue to be that the salting liquid 33.3L of 2M squeezes into reactor by 8852g nickelous sulfate, 4792g cobaltous sulfate, 2818g manganese sulfate compound concentration, inject reactor completely to salting liquid, precursor power has reacted.By the solidliquid mixture after having reacted by centrifugation, wash and at 120 DEG C, dry 24h to neutrality.By presoma and the lithium carbonate after drying in molar ratio 1: 1.05 mix after in Muffle furnace 850 DEG C of roasting 16h, the material after roasting obtains homogeneous single-stage nucleocapsid Li [(Ni after fragmentation is sieved 0.8co 0.1mn 0.1) 1/3(Ni 0.5co 0.25mn 0.25) 2/3] O 2.This material is made 2032 button cells test.
Embodiment 4:
With the salting liquid 36.7L that 12394g nickelous sulfate, 2874g cobaltous sulfate, 1690g manganese sulfate compound concentration are 2M.The solution prepared is injected with the speed of 1.5L/h the reactor that rotating speed is 400rps, inject the NaOH solution of 4M simultaneously, note regulating aqueous slkali flow velocity, keep pH value between 10-11, reactor is injected completely to salting liquid, continue to be that the salting liquid 13.3L of 2M squeezes into reactor by 3815g nickelous sulfate, 2551g cobaltous sulfate, 1610g manganese sulfate compound concentration, inject reactor completely to salting liquid, precursor power has reacted.By the solidliquid mixture after having reacted by centrifugation, wash and at 120 DEG C, dry 24h to neutrality.By presoma and the lithium carbonate after drying in molar ratio 1: 1.05 mix after in Muffle furnace 850 DEG C of roasting 16h, calcined material must homogeneous single-stage nucleocapsid Li [(Ni after fragmentation is sieved 0.7co 0.15mn 0.15) 2/3(Ni 0.4co 0.3mn 0.3) 1/3] O 2.This material is made 2032 button cells test.
Embodiment 5:
With the salting liquid 30L that 3541g nickelous sulfate, 9582g cobaltous sulfate, 2254g manganese sulfate compound concentration are 2M.The solution preparing 30L is injected with the speed of 1.5L/h the reactor that rotating speed is 400rps, inject the NaOH solution of 4M simultaneously, note regulating aqueous slkali flow velocity, keep pH value between 10-11, reactor is injected completely to salting liquid, continue to be that the salting liquid 20L of 2M squeezes into reactor by 2656g nickelous sulfate, 1690g manganese sulfate compound concentration, inject reactor completely to salting liquid, precursor power has reacted.By the solidliquid mixture after having reacted by centrifugation, wash and at 120 DEG C, dry 24h to neutrality.By presoma and the lithium carbonate after drying in molar ratio 1: 1.05 mix after in Muffle furnace 950 DEG C of roasting 16h, the material after roasting obtains homogeneous multistage nucleocapsid Li [(Ni after fragmentation is sieved 2/9co 5/9mn 2/9) 0.6(Ni 0.5mn 0.5) 0.4] O 2.This material is made 2032 button cells test.
Embodiment 6:
With the salting liquid 25L that 6639g nickelous sulfate, 7187g cobaltous sulfate compound concentration are 2M.The solution prepared is injected with the speed of 1.5L/h the reactor that rotating speed is 400rps, inject the NaOH solution of 4M simultaneously, note regulating aqueous slkali flow velocity, keep pH value between 10-11, reactor is injected completely to salting liquid, continue to be that the salting liquid 10L of 2M squeezes into reactor by 6639g nickelous sulfate, 4226g manganese sulfate compound concentration, inject reactor completely to salting liquid, precursor power has reacted.By the solidliquid mixture after having reacted by centrifugation, wash and at 120 DEG C, dry 24h to neutrality.By presoma and the lithium carbonate after drying in molar ratio 1: 1.05 mix after in Muffle furnace 900 DEG C of roasting 16h, the material after roasting obtains homogeneous single-stage nucleocapsid Li [(Ni after fragmentation is sieved 0.5co 0.5) 0.5(Ni 0.5mn 0.5) 0.5] O 2.This material is made 2032 button cells test.
Embodiment 7:
With the salting liquid 30L that 8105g nickelous sulfate, 2713 cobaltous sulfates, 1650g manganese sulfate compound concentration are 2M.The solution preparing 25L is injected with the speed of 1.5L/h the reactor that rotating speed is 400rps, inject the NaOH solution of 4M simultaneously, note regulating aqueous slkali flow velocity, keep pH value between 10-11, reactor is injected completely to salting liquid, continue to be that the salting liquid 25L of 2M squeezes into reactor by 5312g nickelous sulfate, 2808g cobaltous sulfate, 2113g manganese sulfate compound concentration, inject reactor completely to salting liquid, precursor power has reacted.By the solidliquid mixture after having reacted by centrifugation, wash and at 120 DEG C, dry 24h to neutrality.By presoma and the lithium carbonate after drying in molar ratio 1: 1.05 mix after in Muffle furnace 900 DEG C of roasting 16h, after roasting, material must homogeneous single-stage nucleocapsid Li [(Ni after fragmentation is sieved 0.6co 0.2mn 0.2) 0.5(Ni 0.4co 0.2mn 0.4) 0.5] O 2.This material is made 2032 button cells test.
Embodiment 8:
With the salting liquid 40L that 19121g nickelous sulfate, 1150g cobaltous sulfate, 676g manganese sulfate compound concentration are 2M.The solution prepared is injected with the speed of 1.5L/h the reactor that rotating speed is 400rps, inject the NaOH solution of 4M simultaneously, note regulating aqueous slkali flow velocity, keep pH value between 10-11, reactor is injected completely to salting liquid, continue to be that the salting liquid 25L of 2M squeezes into reactor by 1770g nickelous sulfate, 1915g cobaltous sulfate, 1123g manganese sulfate compound concentration, inject reactor completely to salting liquid, precursor power has reacted.By the solidliquid mixture after having reacted by centrifugation, wash and at 120 DEG C, dry 24h to neutrality.By presoma and the lithium carbonate after drying in molar ratio 1: 1.05 mix after in Muffle furnace 780 DEG C of roasting 16h, after roasting, material must homogeneous single-stage nucleocapsid Li [(Ni after fragmentation is sieved 0.9co 0.05mn 0.05) 0.8(Ni 1/3co 1/3mn 1/3) 0.2] O 2.This material is made 2032 button cells test.
Embodiment 9:
With the salting liquid 35L that 14872g nickelous sulfate, 4024 cobaltous sulfate compound concentrations are 2M.Inject with the speed of 1.5L/h the reactor that rotating speed is 400rps by preparing solution, inject the NaOH solution of 4M simultaneously, note regulating aqueous slkali flow velocity, keep pH value between 10-11, reactor is injected completely to salting liquid, continue to be that the salting liquid 15L of 2M squeezes into reactor by 5311g nickelous sulfate, 3381g manganese sulfate compound concentration, inject reactor completely to salting liquid, precursor power has reacted.By the solidliquid mixture after having reacted by centrifugation, wash and at 120 DEG C, dry 24h to neutrality.By presoma and the lithium carbonate after drying in molar ratio 1: 1.05 mix after in Muffle furnace 800 DEG C of roasting 16h, after roasting, material must homogeneous single-stage nucleocapsid Li [(N after fragmentation is sieved i0.8co 0.2) 0.7(Ni 0.5mn 0.5) 0.3] O 2.This material is made 2032 button cells test.
Above-described embodiment 1-4 is for using Phase Diagram Analysis method to LiN 0.6co 0.2mn 0.2o 2homogeneous phase ternary material carry out the instantiation of nucleocapsid structure design, its core is high power capacity district material and shell is high place of safety material.
Above-described embodiment 5-9 is the instantiation using Phase Diagram Analysis method other common materials to be carried out to nucleocapsid structure design.What wherein the nuclear material of embodiment 5 and embodiment 6 was selected is that high density area material shell material in phasor is chosen as high place of safety material; And the core of material is the high power capacity district material in phasor in embodiment 7-9, shell is chosen as high place of safety material.
Can see from the SEM figure of Fig. 1 comparative example 1, embodiment 2, embodiment 5, embodiment 8, synthesized material microstructure is composite material of core-shell structure, is that ball-type or class are spherical under Electronic Speculum.
From Fig. 2 embodiment 5, embodiment 8, embodiment 9, we also can see, synthesized core-shell material has higher specific capacity.
As can see from Figure 3, under the voltage range of 3.0-4.3V, embodiment 1-4 has good cycle performance compared to comparative example 1, and therefore Core-shell structure material can improve the cycle performance of material.
From Fig. 4-7, the Core-shell structure material of the heterogeneity synthesized by us has good cycle performance.
Know from Fig. 8-9, with Li [Ni 0.8co 0.1mn 0.1] O 2for core, with Li [Ni 1/3co 1/3mn 1/3] O 2for the single-stage core-shell material (embodiment 2) of shell synthesis, compare its average assay LiN 0.6co 0.2mn 0.2o 2(comparative example 1), has more excellent high rate performance and thermal stability.
To sum up, based on the method for phase G-Design ternary material nucleocapsid structure, then use the nucleocapsid structure tertiary cathode material for lithium rechargeable battery of this kind of method design, according to the difference of nickel cobalt manganese content separately on the impact of positive pole material property, design 1 >=Ni >=0.7, high power capacity district, 0≤Co≤0.3 that its nucleus is positioned at phasor, its sheathing material is positioned at the positive electrode of 1/3≤Ni≤0.5, high security region, 1/3≤Mn≤0.5.Therefore the tertiary cathode material designed has following molecular composition: Li [(Ni nco 1-m-nmn m) b(Ni cco dmn 1-c-d) a] O 2, and Li (Ni nco 1-m-nmnm) bo 2for the shell structure of this ternary material, wherein, 0≤a, b≤1 and a+b=1,1/3≤n≤0.5,1/3≤m≤0.5,1>=d>=0.7,0≤c≤0.3 and d+c≤1, material has the composite attribute of high security and high-capacity material.The nucleocapsid structure designed is by the complementation of nucleocapsid function, this core-shell material can be made to show height ratio capacity and high stable circulation, high security feature, and material is cheap for manufacturing cost on a large scale, cost does not increase compared with homogeneous phase multicomponent material, and it is repeatable high, lot stability is good, is convenient to the needs that the features such as production management are suitable for large-scale commercial application.
Although invention has been described for composition graphs above; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; instead of it is restrictive; those of ordinary skill in the art is under enlightenment of the present invention; when not departing from present inventive concept, can also make a lot of distortion, these all belong within protection of the present invention.

Claims (10)

1., based on the ball-type of nickel-cobalt-manganese ternary Phase Diagram Analysis or a method for designing for class ball-shaped lithium-ion battery material nucleocapsid structure, it is characterized in that:
With LiNiO 2, LiCoO 2and LiMnO 2for equilateral triangle three summits; And,
At LiNiO 2summit place; The content that Ni content is set to 1, Co and Mn is set to 0 respectively;
At LiCoO 2summit place: the content that Co content is set to 1, Ni and Mn is set to 0 respectively;
At LiMnO 2summit place: the content that Mn content is set to 1, Co and Ni is set to 0;
Molecular formula then in equilateral triangle representated by any point is expressed as Li (Ni xco ymn 1-x-y) O 2,
Wherein, 0≤x, y≤1.
2., according to claim 1 based on the ball-type of nickel-cobalt-manganese ternary Phase Diagram Analysis or the method for designing of class ball-shaped lithium-ion battery material nucleocapsid structure, it is characterized in that:
The region of division 1 >=Ni >=0.6,0≤Co≤0.3,0≤Mn≤0.3 is high power capacity district; Division 1/3≤Ni≤0.5,1/3≤Mn≤0.5, region, 0≤Co≤1/3 are high security district; Division 1/2≤Co≤1,0≤Ni≤1/4,0≤Mn≤1/4 are high density area.
3. according to claim 1 or 2 based on the method for designing of the ball-type of nickel-cobalt-manganese ternary Phase Diagram Analysis or class ball-shaped lithium-ion battery material nucleocapsid structure, it is characterized in that:
Be Li [Ni by molecular formula xco ymn 1-x-y] O 2, wherein, the material of 0≤x, y≤1 projects in ternary phase diagrams according to the content of nickel cobalt manganese, and represents with O point;
Draw one through the line segment AB of this O point, the terminal A of this line segment AB is projected to high security region, the terminal B of this line segment AB is projected to high capacity regions or high-pressure solid region;
Using the composition of the coordinate of described terminal A in high security region as shell material, using the composition of the coordinate of described terminal B in high capacity regions or high-pressure solid region as nuclear material;
The mol ratio of described shell material and described nuclear material is b: a, and wherein, a is OA line segment length, and b is OB line segment length; Then:
Based on nickel-cobalt-manganese ternary Phase Diagram Analysis to the molecular formula after the nucleocapsid structure design of this ternary material be:
Li [(Ni nco 1-m-nmn m) b(Ni ccodMn 1-c-d) a] O 2, wherein 0≤a, b≤1 and a+b=1;
Li (Ni nco 1-m-nmnm) bo 2for the shell structure of this ternary material, wherein, 1/3≤≤ n≤0.5,1/3≤m≤0.5;
Li (Ni dcocMn 1-c-d) aO 2for the nuclear structure of this ternary material, according to be divided into different with high-pressure solid sexual function of ternary material high security:
When needs high-capacity material performance, 1 >=d >=0.6,0≤c≤0.3 and d+c≤1;
When needs high-pressure solid material property, 1/2≤c≤1,0≤d≤1/4 and d+c≤1.
4. the ball-type designed based on the ball-type of nickel-cobalt-manganese ternary Phase Diagram Analysis or the method for designing of class ball-shaped lithium-ion battery material nucleocapsid structure according to claim 3 or class spherical nucleocapsid lithium ion battery material, is characterized in that:
Structural formula is characterized as: Li [(Ni nco 1-m-nmn m) b(Ni cco dmn 1-c-d) a] O 2, wherein 0≤a, b≤1 and a+b=1,1/3≤n≤0.5,1/3≤m≤0.5,1>=d>=0.7,0≤c≤0.3 and d+c≤1; And there is following molecular formula composition:
Li(Ni 0.6Co 0.2Mn 0.2)O 2。
5. ball-type or class spherical nucleocapsid lithium ion battery material according to claim 4, is characterized in that:
It is spherical that this material is ball-type or class under Electronic Speculum.
6. ball-type or class spherical nucleocapsid lithium ion battery material according to claim 5, is characterized in that:
The diameter of described ball-type or class spherical nucleocapsid composite material is 6-50um, and the thickness of shell structure accounts for the 6-40% of ball-type or class spherical nucleocapsid composite material diameter.
7. ball-type or class spherical nucleocapsid lithium ion battery material presoma according to claim 4, is characterized in that:
There is following molecular formula composition:
[(Ni nCo 1-m-nMn m)b(NicCodMn 1-c-d) a](OH) 2
Wherein, 0≤a, b≤1 and a+b=1,1/3≤n≤0.5,1/3≤m≤0.5,1 >=d >=0.7,0≤c≤0.3 and d+c≤1.
8. the preparation method of ball-type or class spherical nucleocapsid lithium ion battery material presoma according to claim 7, concrete steps are as follows:
(1) in reactor, nickel, cobalt and manganese ternary salting liquid A is added with given pace, wherein, mol ratio=c: the d of Ni: Co: Mn: (1-c-d), wherein, d+c≤1; Between 10-12, carry out coprecipitation reaction by aqueous slkali control ph and obtain solidliquid mixture, the molecular formula of precipitated solid is (Ni cco dmn 1-c-d) (OH) 2, thus form the core of presoma;
(2) at the uniform velocity continue to inject nickel, cobalt and manganese ternary solution B with given pace, wherein, mol ratio=n: 1-n-m: the m of Ni: Co: Mn, 1/3≤n≤0.5,1/3≤m≤0.5, form the housing parts of the presoma be coated on outside above-mentioned presoma core thus;
(3) solidliquid mixture after step (2) having been reacted is separated by centrifugal filtration, washs and at 60-200 DEG C, dry 4-10h to neutrality; The precipitated solid gross formula obtained is (Ni 0.6co 0.2mn 0.2) (HO) 2, this precipitated solid is nucleocapsid structure ternary material precursor.
9., for a nucleocapsid structure ternary material for anode material for lithium-ion batteries, it is characterized in that:
After according to Claim 8, the nucleocapsid structure ternary material precursor obtained is pulverized and lithium source is baking mixed obtains.
10., according to claim 9 for the nucleocapsid structure ternary material of anode material for lithium-ion batteries, it is characterized in that:
Nucleocapsid structure ternary material precursor that claim 8 is obtained pulverize after with lithium carbonate in molar ratio 1: 1 ~ 1: 1.2 mix after multistage roasting in Muffle furnace, its sintering temperature 600-1000 DEG C, roasting time 8-30h, after multistage roasting through cooling, broken, sieve to obtain nucleocapsid structure ternary material.
CN201410137902.XA 2014-04-02 2014-04-02 Core-shell structure positive material based on phase diagram design and design method of core-shell structure positive material Pending CN104979528A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410137902.XA CN104979528A (en) 2014-04-02 2014-04-02 Core-shell structure positive material based on phase diagram design and design method of core-shell structure positive material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410137902.XA CN104979528A (en) 2014-04-02 2014-04-02 Core-shell structure positive material based on phase diagram design and design method of core-shell structure positive material

Publications (1)

Publication Number Publication Date
CN104979528A true CN104979528A (en) 2015-10-14

Family

ID=54275826

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410137902.XA Pending CN104979528A (en) 2014-04-02 2014-04-02 Core-shell structure positive material based on phase diagram design and design method of core-shell structure positive material

Country Status (1)

Country Link
CN (1) CN104979528A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105891243A (en) * 2016-03-30 2016-08-24 上海大学 Two-dimensional continuous component sample, and preparing method and application thereof in quick determination of phase diagram high flux
CN107359319A (en) * 2017-05-27 2017-11-17 中国电力科学研究院 A kind of lithium-rich manganese-based layered cathode material and preparation method thereof
CN108539193A (en) * 2018-05-15 2018-09-14 北京科技大学 Include the nucleocapsid NCM tertiary cathode materials and preparation method thereof of carbon nanotube

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1723576A (en) * 2001-11-22 2006-01-18 株式会社汤浅 Positive electrode active material for lithium secondary cell and lithium secondary cell
CN101809788A (en) * 2007-11-06 2010-08-18 松下电器产业株式会社 Positive electrode active material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery comprising the same
CN102244256A (en) * 2011-06-07 2011-11-16 中信国安盟固利动力科技有限公司 Cathode active material with core shell structure, preparation method and secondary battery using material
CN102347483A (en) * 2011-10-11 2012-02-08 上海中兴派能能源科技有限公司 Multilayer composite ternary material and precursor thereof as well as preparation method of multilayer composite ternary material and precursor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1723576A (en) * 2001-11-22 2006-01-18 株式会社汤浅 Positive electrode active material for lithium secondary cell and lithium secondary cell
CN101809788A (en) * 2007-11-06 2010-08-18 松下电器产业株式会社 Positive electrode active material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery comprising the same
CN102244256A (en) * 2011-06-07 2011-11-16 中信国安盟固利动力科技有限公司 Cathode active material with core shell structure, preparation method and secondary battery using material
CN102347483A (en) * 2011-10-11 2012-02-08 上海中兴派能能源科技有限公司 Multilayer composite ternary material and precursor thereof as well as preparation method of multilayer composite ternary material and precursor

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105891243A (en) * 2016-03-30 2016-08-24 上海大学 Two-dimensional continuous component sample, and preparing method and application thereof in quick determination of phase diagram high flux
CN105891243B (en) * 2016-03-30 2018-10-23 上海大学 Two-dimentional continuous component sample, preparation method and its application in the high-throughput quickly measurement of phasor
CN107359319A (en) * 2017-05-27 2017-11-17 中国电力科学研究院 A kind of lithium-rich manganese-based layered cathode material and preparation method thereof
CN108539193A (en) * 2018-05-15 2018-09-14 北京科技大学 Include the nucleocapsid NCM tertiary cathode materials and preparation method thereof of carbon nanotube

Similar Documents

Publication Publication Date Title
CN104157831B (en) Lithium-rich manganese-based composite positive pole of the spinel nickel LiMn2O4 of a kind of core shell structure, stratiform and preparation method thereof
CN103840151B (en) Tertiary cathode material of a kind of special mono-crystalline structures and preparation method thereof
CN104393285B (en) Nickel-cobalt-aluminum ternary positive electrode material and its preparation method
CN104037404B (en) A kind of lithium ion battery nickel cobalt aluminum lithium and LiMn2O4 composite and preparation method thereof
CN108767239A (en) A kind of nickelic low cobalt tertiary cathode material and preparation method thereof
CN102751470B (en) Preparation method of lithium ion battery high-voltage composite cathode material
CN102983326B (en) Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method
CN103762353B (en) A kind of heterogeneous nucleocapsid structure high-capacity lithium ion battery electricity positive electrode with and preparation method thereof
CN103280574A (en) Lithium-enriched ternary anode material of power lithium-ion battery and preparation method of lithium-enriched ternary anode material
CN105140482B (en) A kind of modification lithium-ion battery anode material and preparation method thereof
CN102916171B (en) Concentration-gradually-changed spherical lithium nickel manganese oxide cathode material and preparation method thereof
CN107611384B (en) High-performance concentration gradient high-nickel material, preparation method thereof and application thereof in lithium ion battery
CN103474650A (en) Method for preparing hollow high voltage nickel manganese acid lithium anode material
CN104916837A (en) Preparation method of aluminum element doped ternary positive electrode material
CN103794782B (en) A kind of lithium-rich manganese base material, its preparation method and lithium ion battery
CN104577096A (en) Cathode material for lithium-ion battery, preparation method of cathode material and battery
CN102122712A (en) Method for preparing high-compaction high-voltage lithium cobaltite cathode material
CN102637867A (en) Chromium-doped lithium-nickel-manganese-oxygen material and preparation method thereof, and lithium ion battery containing chromium-doped lithium-nickel-manganese-oxygen material
CN102583583B (en) A kind of lithium ion battery manganese cobalt lithium oxide anode material and preparation method thereof
CN103647070B (en) A kind of rare earth samarium is modified the preparation method of tertiary cathode material
CN102664253A (en) Lithium-rich material and preparation method thereof and lithium ion battery containing same
CN107069013B (en) Modified lithium-rich manganese-based positive electrode material and preparation method thereof
CN104078669A (en) Preparation method of multi-component positive electrode material
CN102832387B (en) Layer-structured ternary material with rich lithium and high manganese as well as preparation method and application thereof
CN103928660A (en) Preparation method of multi-element anode material with multi-level structure

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20151014

WD01 Invention patent application deemed withdrawn after publication