CN1870331A - Secondary ball lithium nickel manganese oxygen plus plate material for lithium ion battery and its preparation method - Google Patents
Secondary ball lithium nickel manganese oxygen plus plate material for lithium ion battery and its preparation method Download PDFInfo
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- CN1870331A CN1870331A CNA2006100109921A CN200610010992A CN1870331A CN 1870331 A CN1870331 A CN 1870331A CN A2006100109921 A CNA2006100109921 A CN A2006100109921A CN 200610010992 A CN200610010992 A CN 200610010992A CN 1870331 A CN1870331 A CN 1870331A
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Abstract
A method for preparing secondary ball LiNiMnCoO positive electrode material used on lithium ion cell includes utilizing cocrystallization means to synthesize secondary ball NiMnCo hydroxide under ammonia condition; obtaining secondary ball NiMnCoO compound after baking and decomposing; combining Ni-Co-Mn-O by chemical bond and mixing NiMnCoO compound with lithium salt uniformly; obtaining secondary ball LiNiMnCoO compound after low temperature baking, activating treatment of material, high temperature burning, cooling and grinding.
Description
Technical field
The invention belongs to the energy and material preparing technical field, be specifically related to a kind of lithium ion battery low-cost and high-performance secondary ball nickel manganese oxygen plus plate material for lithium and preparation method thereof.
Background technology
Lithium ion battery because of characteristics such as it has high voltage, energy density is big, capacity is big, self-discharge rate is little, have extended cycle life, memory-less effect, serviceability temperature scope are wide, non-environmental-pollutions, is the charge power supply of high-grade electronic product first-selection, is widely used.The composite oxides such as the LiCoO of lithium and transition metal (as Co, Ni, Mn etc.)
2, LiNiO
2, LiMn
2O
4All can do the positive electrode of lithium ion battery.The cobalt acid lithium (LiCoO of layer structure
2) use at most, also have the lithium nickelate (LiNiO of layer structure
2) and the LiMn2O4 (LiMn of spinel structure
2O
4).The index of estimating them has reversible capacity, platform voltage, cyclical stability, fail safe and price etc.The advantage of cobalt acid lithium is a function admirable, the capacity height (148～158mAh/g), platform voltage good (3.8V Vs Li), preparation technology is simple relatively, shortcoming be cost an arm and a leg, poor safety performance; The advantage capacity height of lithium nickelate (170～190mAh/g), moderate cost, shortcoming is that the stable circulation performance is poor, poor safety performance, platform voltage low (3.6V VsLi), the preparation process complexity; The advantage of LiMn2O4 is that security performance is good, cheap, platform voltage high (4.0V Vs Li), and shortcoming is that high-temperature behavior is poor, and capacity is on the low side (being about 120mAh/g).
Reduce cost, improve quality, manufacture excellent performance and low-cost positive electrode is one of key issue of high capacity lithium ion battery development.Carry out doping vario-property to reduce cost for cobalt acid lithium more,, mix metal element A l, Ni etc. as 99119446.2 kinds of Chinese patents; Mix metallic elements such as Co, Cr and improve structural stability or outside particle, coat layer of substance contacting for adopt of lithium nickelate and LiMn2O4 more with isolated and electrolyte, as United States Patent (USP) 6274272,6551571, Chinese patent application 00117347.2 or the like, to introduce other compositions but mix and coat, bring greater loss to capacity.Therefore, the close low-cost anode material for lithium-ion batteries of research and development electrical property and cobalt acid lithium has become the important research direction of lithium ion battery development.
In recent years, the someone adopts with nickel oxide (NiO), manganese dioxide (MnO
2) and cobaltosic oxide (Co
3O
4) powder is initial feed, after mixing by physical mechanical, adds lithium carbonate (Li
2CO
3), prepare nickel manganese oxygen plus plate material for lithium through solid-phase sintering, to reduce cost.Yet, owing to adopt single metal oxide powder, must bring the inhomogeneities of material, thereby cause product behind the sintering to be difficult to obtain not having the material of dephasign by the simple physics mechanical mixture, make capacity attenuation fast, defectives such as comprehensive electrochemical properties reduction.In addition, adopt this method, many important physical indexs of each metal oxide such as granular size, shape characteristic etc. are all needed to be strict with and control, this is to bringing very big difficulty on the production application.
Summary of the invention
The present invention has overcome the deficiency of previous materials and method, provides that a kind of cost is low, tap density is high, specific capacity is big, good cycle, stay in grade, material that preparation technology is easy and preparation method thereof.
The lithium ion battery of the present invention's exploitation low-cost and high-performance laminated Li-Ni manganese oxygen plus plate material, with and raw material nickel manganese cobalt complex metal hydroxide and oxide, nickel～cobalt in this compound～manganese～oxygen is to mix by the combination of chemical bond rather than simple physics.Nickel manganese cobalt complex metal hydroxide is to produce by the precipitation method with nickeliferous, cobalt, manganese salt solution, obtains spherical Ni-Mn-Co-O thing after the roasting.With this spherical Ni-Mn-Co-O thing is that raw material and lithium salts fully are mixed by a certain percentage, adopts unique process for solid phase synthesis to prepare the stratiform nickel manganese oxygen plus plate material for lithium.
The inventive method comprises the following steps:
(1), Ni: Mn: Co=1 in molar ratio: 1: 0～1 preparing metal total concentration be 1～1.5mol/L+the divalent nickel salt ,+divalent manganese salt and+mixed aqueous solution of divalent cobalt salt; Compound concentration is the NaOH solution of 1～10mol/L; Compound concentration is the NH of 5～10mol/L
4 +Solion;
(2), with above-mentioned mixed aqueous solution and NH
4 +Solion evenly joins in the reactor of band stirring continuously, and control contains NH
4 +The addition of the compound of ion is mol ratio NH
4 +/ (Ni+Mn+Co)=2～8: 1, the effect of ammonia is and cobalt, nickel, manganese complexing the formation speed and the shape of control hydroxide; Adding NaOH solution is 9.0～13.0 with the control pH value in reaction; Reaction temperature is at 30～90 ℃; Reacted after 20～30 hours ageing 10～20 hours, the pH of control ageing process is consistent with the pH of course of reaction; Separating also, washing precipitation gets secondary ball nickel magnesium cobalt hydroxide; The speed of its mixing speed directly affects the hydroxide particle diameter, along with the increase particle diameter of stirring intensity diminishes;
(3), at 400～900 ℃ of above-mentioned secondary ball of roasting temperature nickel magnesium cobalt hydroxides, calcination time is 3～15 hours,, 1～10 ℃/min of heating rate decomposes and to obtain secondary ball Ni-Mn-Co-O compound;
(4), be 0.95～1.15 to mix the secondary ball Ni-Mn-Co-O compound that makes according to the mol ratio of Li/ (Ni+Mn+Co) with lithium salts, at 400～700 ℃ of following low-temperature bake 5～20hr, fine grinding is carried out to material in the cooling back, improve the material surface activity, under 800～1100 ℃, carry out high-temperature calcination again, 1～10 ℃/min of heating rate, calcination time 5～20hr obtains the lithium-nickel-manganese-cobalt oxygen compound of secondary spherical structure after the cooling.
Wherein: lithium salts can be LiOHH
2O, LiNO
3Or Li
2CO
3Nickel salt, manganese salt and cobalt salt can be a kind of in sulfate, nitrate and the chloride or two kinds.
Spherical nickel magnesium cobalt hydroxide has special secondary spherical structure, and granule is closely arranged on subsphaeroidal aggregation and surface, and this coating of particles is sheet, strip, closely spherical, and the specific area of this multi-element metal hydroxide is 5～50m
2/ g, tap density is 1.0～2.0g/cm
3, middle particle diameter is 5～20 μ m.Spherical Ni-Mn-Co-O compound has special secondary spherical structure, and granule is closely arranged on promptly subsphaeroidal aggregation and surface, and this coating of particles is sheet, strip, closely spherical, and this multi-element metal oxide specific area is 2～25m
2/ g, tap density is 1.2～2.5g/cm
3, middle particle diameter is 5～20 μ m.
The lithium-nickel-manganese-cobalt oxygen compound has the secondary spherical structure, and its chemical formula is: LiNi
xMn
xCo
1-2xO
2, x=0.3～0.5 wherein.Lithium-nickel-manganese-cobalt oxygen compound specific area is 0.2～0.8m
2/ g, tap density 2.0～2.6g/cm
3, middle particle diameter is 5～15 μ m, its microstructure is a secondary ball aggregation.The lithium-nickel-manganese-cobalt oxygen compound has 4.5～3.0V continuous discharge voltage characteristic with respect to lithium anode, and specific discharge capacity reaches 168mAh/g, and average every circulation primary capacity attenuation rate is 0.05～0.1%.
The invention has the beneficial effects as follows: cocrystallization obtains uniform nickel magnesium cobalt hydroxide under the ammonia environment, nickel-cobalt in this compound-manganese-oxygen is to mix by the combination of chemical bond rather than simple physics, microstructure shows the secondary spherical looks, secondary ball nickel manganese oxygen plus plate material for lithium tap density height, the specific discharge capacity prepared with this presoma reaches 168mAh/g (4.5V vs.Li), preparation technology is easy, cost is low, especially is fit to large-scale lithium ion battery and uses.
Description of drawings
Fig. 1 is the sem photograph of secondary ball nickel magnesium cobalt hydroxide;
Fig. 2 is the sem photograph of secondary ball Ni-Mn-Co-O compound;
Fig. 3 is a secondary ball lithium-nickel-manganese-cobalt oxygen compound sem photograph;
Embodiment
Embodiment one
Ni: Mn: Co=1 in molar ratio: cobaltous sulfate, nickelous sulfate, manganese sulfate mixed aqueous solution that 1: 1 preparing metal total concentration is 1mol/L; Compound concentration is the NaOH solution of 10mol/L; Compound concentration is the NH of 10mol/L
4 +Solion;
With above-mentioned mixed aqueous solution and NH
4 +Solion evenly joins in the reactor of band stirring continuously, and control contains NH
4 +The addition of the compound of ion is mol ratio NH
4 +/ (Ni+Mn+Co)=4: 1; Adding NaOH solution is 13.0 with the control pH value in reaction; Reaction temperature is at 90 ℃; Reacted after 20 hours ageing 20 hours, the pH of control ageing process is consistent with the pH of course of reaction; Separation and washing precipitation get secondary ball nickel magnesium cobalt hydroxide, record tap density 1.70g/cm
3, specific area is 9.6m
2/ g, middle particle diameter D
50=7.2 μ m.
At the 400 ℃ of above-mentioned secondary ball of roasting temperature nickel magnesium cobalt hydroxides, calcination time is 15 hours, and cooling is broken, 10 ℃/min of heating rate, and decomposition obtains secondary ball Ni-Mn-Co-O compound, records tap density 1.80g/cm
3, specific area is 18m
2/ g, middle particle diameter D
50=8.31 μ m.
Get the secondary ball Ni-Mn-Co-O compound that 40g makes, according to the mol ratio of Li/ (Ni+Mn+Co) is 0.95 to mix with lithium salts, at 700 ℃ of following low-temperature bake 5hr, high-temperature calcination is carried out, 10 ℃/min of heating rate again to material fine grinding 30 minutes in autogenous mill in cooling back under 1100 ℃, calcination time 5hr, obtain the lithium-nickel-manganese-cobalt oxygen compound of secondary spherical structure after the cooling, have tangible secondary spherical structure, its chemical formula is LiNi
1/3Mn
1/3Co
1/3O
2, record tap density 2.35g/cm
3, specific area is 0.46m
2/ g, middle particle diameter D
50=8.5 μ m.
Gained secondary ball lithium-nickel-manganese-cobalt oxygen compound is dressed up simulated battery, and barrier film is the celgard2300 type, and negative pole is a metal lithium sheet.Recording specific discharge capacity is 168mAh/g (4.5V vs.Li), after 20 circulations, and specific capacity decay 1.30%.
Embodiment two
Ni: Mn=1 in molar ratio: 1 preparing metal total concentration is the nickelous sulfate of 1mol/L, the mixed aqueous solution of manganese sulfate; Compound concentration is the NaOH solution of 1mol/L; Compound concentration is the NH of 5mol/L
4 +Solion;
With above-mentioned mixed aqueous solution and NH
4 +Solion evenly joins in the reactor of band stirring continuously, and control contains NH
4 +The addition of the compound of ion is mol ratio NH
4 +/ (Ni+Mn)=2: 1; Adding NaOH solution is 9.0 with the control pH value in reaction; Reaction temperature is at 90 ℃; Reacted after 30 hours ageing 20 hours, the pH of control ageing process is consistent with the pH of course of reaction; Separation and washing precipitation get secondary ball nickel manganese hydroxide, record tap density 1.75g/cm
3, specific area is 9.1m
2/ g, middle particle diameter D
50=7.2 μ m.
At the 400 ℃ of above-mentioned secondary ball of roasting temperature nickel manganese hydroxide, calcination time is 15 hours, 1 ℃/min of heating rate, and the cooling fragmentation makes secondary ball nickel manganese and oxygen compound, tap density 1.89g/cm
3, specific area is 16m
2/ g, middle particle diameter D
50=8.51 μ m.
Get above-mentioned nickel manganese and oxygen compound 40g, according to the mol ratio of Li/ (Ni+Mn) is 1.15 to mix with lithium salts, at 700 ℃ of following low-temperature bake 20hr, the fine grinding 30 minutes in autogenous mill of cooling back is carried out high-temperature calcination, 3 ℃/min of heating rate again under 800 ℃, calcination time 20hr, obtain the Li-Ni-Mn-O compound of secondary spherical structure after the cooling, have tangible secondary spherical structure, its chemical formula is LiNi
1/2Mn
1/2O
2, record tap density 2.05g/cm
3, specific area is 0.48m
2/ g, middle particle diameter D
50=9.1 μ m.
Gained secondary ball Li-Ni-Mn-O compound is dressed up simulated battery, and barrier film is the celgard2300 type, and negative pole is a metal lithium sheet.Recording specific discharge capacity is 146mAh/g (4.3V vs.Li), after 20 circulations, and specific capacity decay 1.30%.
Embodiment three
Ni: Mn: Co=1 in molar ratio: cobaltous sulfate, nickelous sulfate, manganese sulfate mixed aqueous solution that 1: 0.5 preparing metal total concentration is 1.5mol/L; Preparing dense tall building is the NaOH solution of 8mol/L; Compound concentration is the NH of 5mol/L
4 +Solion;
With above-mentioned mixed aqueous solution and NH
4 +Solion evenly joins in the reactor of band stirring continuously, and control contains NH
4 +The addition of the compound of ion is mol ratio NH
4 +/ (Ni+Mn+Co)=8: 1; Adding NaOH solution is 9.0 with the control pH value in reaction; Reaction temperature is at 30 ℃; Reacted after 20 hours ageing 20 hours, the pH of control ageing process is consistent with the pH of course of reaction; Separation and washing precipitation get secondary ball nickel magnesium cobalt hydroxide, record tap density 1.55g/cm
3, specific area is 12.6m
2/ g, middle particle diameter D
50=6.2 μ m.
At the 900 ℃ of above-mentioned secondary ball of roasting temperature nickel magnesium cobalt hydroxides, calcination time is 3 hours,, 10 ℃/min of heating rate, decomposition obtains secondary ball Ni-Mn-Co-O compound, records tap density 1.70g/cm
3, specific area is 18.9m
2/ g, middle particle diameter D
50=8.01 μ m.
Is 1 to mix with lithium salts the secondary ball Ni-Mn-Co-O compound that makes according to the mol ratio of Li/ (Ni+Mn+Co), at 700 ℃ of following low-temperature bake 20hr, the fine grinding 30 minutes in autogenous mill of cooling back, under 1100 ℃, carry out high-temperature calcination again, 1～10 ℃/min of heating rate, calcination time 5hr obtains the lithium-nickel-manganese-cobalt oxygen compound of secondary spherical structure after the cooling, have tangible secondary spherical structure, its chemical formula is LiNi
0.4Mn
0.4Co
0.2O
2, record tap density 2.25g/cm
3, specific area is 0.37m
2/ g, middle particle diameter D
50=9.0 μ m.
Gained secondary ball lithium-nickel-manganese-cobalt oxygen compound is dressed up simulated battery, and barrier film is the celgard2300 type, and negative pole is a metal lithium sheet.Recording specific discharge capacity is 164mAh/g (4.5V vs.Li), after 20 circulations, and specific capacity decay 2.00%.
Embodiment four
Ni: Mn: Co=1 in molar ratio: cobalt nitrate, nickel nitrate, manganese nitrate mixed aqueous solution that 1: 0.22 preparing metal total concentration is 1.2mol/L; Compound concentration is the NaOH solution of 4mol/L; Compound concentration is the NH of 8mol/L
4 +Solion;
With above-mentioned mixed aqueous solution and NH
4 +Solion evenly joins in the reactor of band stirring continuously, and control contains NH
4 +The addition of the compound of ion is mol ratio NH
4 +/ (Ni+Mn+Co)=6: 1; Adding NaOH solution is 12.0 with the control pH value in reaction; Reaction temperature is at 30 ℃; Reacted after 30 hours ageing 10 hours, the pH of control ageing process is consistent with the pH of course of reaction; Separation and washing precipitation get secondary ball nickel magnesium cobalt hydroxide, record tap density 1.9g/cm
3, specific area is 7.1m
2/ g, middle particle diameter D
50=6.9 μ m.
At the 900 ℃ of above-mentioned secondary ball of roasting temperature nickel magnesium cobalt hydroxides, calcination time is 8 hours,, 1 ℃/min of heating rate, decomposition obtains secondary ball Ni-Mn-Co-O compound;
With the secondary ball Ni-Mn-Co-O compound 40g that makes, according to the mol ratio of Li/ (Ni+Mn+Co) is 1.1 to mix with lithium salts, at 600 ℃ of following low-temperature bake 10hr, the fine grinding in autogenous mill of cooling back exists after 30 minutes again, carry out high-temperature calcination under 900 ℃, 6 ℃/min of heating rate, calcination time 10hr obtains the lithium-nickel-manganese-cobalt oxygen compound of secondary spherical structure after the cooling, have tangible secondary spherical structure, its chemical formula is LiNi
0.45Mn
0.45Co
0.1O
2, record tap density 2.45g/cm
3, specific area is 0.36m
2/ g, middle particle diameter D
50=9.5 μ m.
Gained secondary ball lithium-nickel-manganese-cobalt oxygen compound is dressed up simulated battery, and barrier film is the celgard2300 type, and negative pole is a metal lithium sheet.Recording specific discharge capacity is 167mAh/g (4.5V vs.Li), after 30 circulations, and specific capacity decay 1.50%.
Embodiment five
Ni: Mn: Co=1 in molar ratio: the mixed aqueous solution of the cobalt nitrate that 1: 0.85 preparing metal total concentration is 1mol/L, nickel nitrate, manganese nitrate; Compound concentration is the NaOH solution of 8mol/L; Compound concentration is the NH of 6mol/L
4 +Solion;
With above-mentioned mixed aqueous solution and NH
4 +Solion evenly joins in the reactor of band stirring continuously, and control contains NH
4 +The addition of the compound of ion is mol ratio NH
4 +/ (Ni+Mn+Co)=4: 1; Adding NaOH solution is 12.0 with the control pH value in reaction; Reaction temperature is at 50 ℃; Reacted after 25 hours ageing 10 hours, the pH of control ageing process is consistent with the pH of course of reaction; Separation and washing precipitation get secondary ball nickel magnesium cobalt hydroxide, record tap density 2.0g/cm
3, specific area is 5.1m
2/ g, middle particle diameter D
50=7.9 μ m.
At the 700 ℃ of above-mentioned secondary ball of roasting temperature nickel magnesium cobalt hydroxides, calcination time is 5 hours,, 1 ℃/min of heating rate, decomposition obtains secondary ball Ni-Mn-Co-O compound, records tap density 2.45g/cm
3, specific area is 5.1m
2/ g, middle particle diameter D
50=9.5 μ m.
With the secondary ball Ni-Mn-Co-O compound 40g that makes, according to the mol ratio of Li/ (Ni+Mn+Co) is 0.98 to mix with lithium salts, at 400 ℃ of following low-temperature bake 20hr, the fine grinding 30 minutes in autogenous mill of cooling back, under 1000 ℃, carry out high-temperature calcination again, 20 ℃/min of heating rate, calcination time 8hr obtains the lithium-nickel-manganese-cobalt oxygen compound of secondary spherical structure after the cooling.Have tangible secondary spherical structure, its chemical formula is LiNi
0.35Mn
0.35Co
0.3O
2, record tap density 2.15g/cm
3, specific area is 0.49m
2/ g, middle particle diameter D
50=8.5 μ m.
Gained secondary ball lithium-nickel-manganese-cobalt oxygen compound is dressed up simulated battery, and barrier film is the celgard2300 type, and negative pole is a metal lithium sheet.Recording specific discharge capacity is 150mAh/g (4.3V vs.Li), after 20 circulations, and specific capacity decay 0.50%.
Embodiment six
Ni: Mn: Co=1 in molar ratio: the mixed aqueous solution of the cobalt chloride that 1: 1 preparing metal total concentration is 1.1mol/L, nickel chloride, manganese nitrate; Compound concentration is the NaOH solution of 2mol/L; Compound concentration is the NH of 8mol/L
4 +Solion;
With above-mentioned mixed aqueous solution and NH
4 +Solion evenly joins in the reactor of band stirring continuously, and control contains NH
4 +The addition of the compound of ion is mol ratio NH
4 +/ (Ni+Mn+Co)=2: 1; Adding NaOH solution is 10.0 with the control pH value in reaction; Reaction temperature is at 50 ℃; Reacted after 26 hours ageing 18 hours, the pH of control ageing process is consistent with the pH of course of reaction; Separation and washing precipitation get secondary ball nickel magnesium cobalt hydroxide, record tap density 1.20g/cm
3, specific area is 15.1m
2/ g, middle particle diameter D
50=9.1 μ m.
At the 800 ℃ of above-mentioned secondary ball of roasting temperature nickel magnesium cobalt hydroxides, calcination time is 7 hours,, 3 ℃/min of heating rate, decomposition obtains secondary ball Ni-Mn-Co-O compound, records tap density 1.6g/cm
3, specific area is 22m
2/ g, middle particle diameter D
50=6.31 μ m.
Is 1 to mix with lithium salts the secondary ball Ni-Mn-Co-O compound that makes according to the mol ratio of Li/ (Ni+Mn+Co), at 550 ℃ of following low-temperature bake 10hr, the fine grinding 30 minutes in autogenous mill of cooling back, under 950 ℃, carry out high-temperature calcination again, 1 ℃/min of heating rate, calcination time 5hr obtains the lithium-nickel-manganese-cobalt oxygen compound of secondary spherical structure after the cooling, have tangible secondary spherical structure, its chemical formula is LiNi
1/3Mn
1/3Co
1/3O
2, record tap density 2.25g/cm
3, specific area is 0.39m
2/ g, middle particle diameter D
50=6.5 μ m.
Gained secondary ball lithium-nickel-manganese-cobalt oxygen compound is dressed up simulated battery, and barrier film is the celgard2300 type, and negative pole is a metal lithium sheet.Recording specific discharge capacity is 148mAh/g (4.3V vs.Li), after 30 circulations, and specific capacity decay 1.85%.
Embodiment seven
Ni: Mn: Co=1 in molar ratio: the mixed aqueous solution of the cobalt chloride that 1: 0.5 preparing metal total concentration is 1.5mol/L, nickel chloride, manganese nitrate; Compound concentration is the NaOH solution of 80mol/L; Prepare the NH that dense tall building is 5mol/L
4 +Solion;
With above-mentioned mixed aqueous solution and NH
4 +Solion evenly joins in the reactor of band stirring continuously, and control contains NH
4 +The addition of the compound of ion is mol ratio NH
4 +/ (Ni+Mn+Co)=8: 1; Adding NaOH solution is 13.0 with the control pH value in reaction; Reaction temperature is at 30 ℃; Reacted after 20 hours ageing 20 hours, the pH of control ageing process is consistent with the pH of course of reaction; Separation and washing precipitation get secondary ball nickel magnesium cobalt hydroxide, record tap density 1.45g/cm
3, specific area is 12.1m
2/ g, middle particle diameter D
50=8.1 μ m.
At the 600 ℃ of above-mentioned secondary ball of roasting temperature nickel magnesium cobalt hydroxides, calcination time is 5 hours,, 1 ℃/min of heating rate, decomposition obtains secondary ball Ni-Mn-Co-O compound, records tap density 1.75g/cm
3, specific area is 20m
2/ g, middle particle diameter D
50=8.31 μ m.
Is 0.98 to mix with lithium salts the secondary ball Ni-Mn-Co-O compound that makes according to the mol ratio of Li/ (Ni+Mn+Co), at 400 ℃ of following low-temperature bake 20hr, the fine grinding 30 minutes in autogenous mill of cooling back, under 900 ℃, carry out high-temperature calcination again, 1 ℃/min of heating rate, calcination time 8hr obtains the lithium-nickel-manganese-cobalt oxygen compound of secondary spherical structure after the cooling, have tangible secondary spherical structure, its chemical formula is LiNi
0.4Mn
0.4Co
0.5O
2, record tap density 2.0g/cm
3, specific area is 0.54m
2/ g, middle particle diameter D
50=6.3 μ m.
Gained secondary ball lithium-nickel-manganese-cobalt oxygen compound is dressed up simulated battery, and the simulated battery septation is the celgard2300 type, and negative pole is a metal lithium sheet.Recording specific discharge capacity is 168mAh/g (4.5V vs.Li), after 20 circulations, and specific capacity decay 1.90%.
Embodiment eight
Ni: Mn: Co=1 in molar ratio: cobaltous sulfate, nickelous sulfate, manganese sulfate mixed aqueous solution that 1: 1 preparing metal total concentration is 1mol/L; Compound concentration is the NaOH solution of 10mol/L; Compound concentration is the NH of 10mol/L
4 +Solion;
With above-mentioned mixed aqueous solution and NH
4 +Solion evenly joins in the reactor of band stirring continuously, and control contains NH
4 +The addition of the compound of ion is mol ratio NH
4 +/ (Ni+Mn+Co)=4: 1; Adding NaOH solution is 13.0 with the control pH value in reaction; Reaction temperature is at 90 ℃; Reacted after 20 hours ageing 20 hours, the pH of control ageing process is consistent with the pH of course of reaction; Separation and washing precipitation get secondary ball nickel magnesium cobalt hydroxide, record tap density 1.70g/cm
3, specific area is 9.6m
2/ g, middle particle diameter D
50=7.2 μ m.
At the 400 ℃ of above-mentioned secondary ball of roasting temperature nickel magnesium cobalt hydroxides, calcination time is 15 hours, and cooling is broken, 10 ℃/min of heating rate, and decomposition obtains secondary ball Ni-Mn-Co-O compound, records tap density 1.80g/cm
3, specific area is 18m
2/ g, middle particle diameter D
50=8.31 μ m.
Get the secondary ball Ni-Mn-Co-O compound that 40g makes, according to the mol ratio of Li/ (Ni+Mn+Co) is 0.95 to mix with lithium salts, at 700 ℃ of following low-temperature bake 5hr, under 1100 ℃, carry out high-temperature calcination after the cooling again, 10 ℃/min of heating rate, calcination time 5hr obtains the lithium-nickel-manganese-cobalt oxygen compound of secondary spherical structure after the cooling, have tangible secondary spherical structure, its chemical formula is LiNi
1/3Mn
1/3Co
1/3O
2, record tap density 2.2g/cm
3, specific area is 0.48m
2/ g, middle particle diameter D
50=8.5 μ m.
Gained secondary ball lithium-nickel-manganese-cobalt oxygen compound is dressed up simulated battery, and barrier film is the celgard2300 type, and negative pole is a metal lithium sheet.Recording its specific capacity is 130mAh/g (4.3V vs.Li), and after 20 circulations, specific capacity has decayed 5.6%.
Claims (4)
1. a lithium ion battery is with secondary ball nickel manganese oxygen plus plate material for lithium, and it is characterized in that: the lithium-nickel-manganese-cobalt oxygen compound has the secondary spherical structure, and its chemical formula is: LiNi
xMn
xCo
1-2xO
2, x=0.3～0.5 wherein.
2. the preparation method of a lithium ion battery usefulness secondary ball nickel manganese oxygen plus plate material for lithium the steps include:
(1), Ni: Mn: Co=1 in molar ratio: 1: 0～1 preparing metal total concentration be 1～1.5mol/L+the divalent nickel salt ,+divalent manganese salt and+mixed aqueous solution of divalent cobalt salt; Compound concentration is the NaOH solution of 1～10mol/L; Compound concentration is the NH of 5～10mol/L
4 +Solion;
(2), with above-mentioned mixed aqueous solution and NH
4 +Solion evenly joins in the reactor of band stirring continuously, and control contains NH
4 +The addition of the compound of ion is mol ratio NH
4 +/ (Ni+Mn+Co)=2～8: 1; Adding NaOH solution is 9.0～13.0 with the control pH value in reaction; Reaction temperature is at 30～90 ℃; Reacted after 20～30 hours ageing 10～20 hours, the pH of control ageing process is consistent with the pH of course of reaction; Separating also, washing precipitation gets secondary ball nickel magnesium cobalt hydroxide;
(3), at 400～900 ℃ of above-mentioned secondary ball of roasting temperature nickel magnesium cobalt hydroxides, calcination time is 3～15 hours, decomposes to obtain secondary ball Ni-Mn-Co-O compound;
(4), be 0.95～1.15 to mix the secondary ball Ni-Mn-Co-O compound that makes according to the mol ratio of Li/ (Ni+Mn+Co) with lithium salts, at 400～700 ℃ of following low-temperature bake 5～20hr, activation processing is carried out to material in the cooling back, under 800～1100 ℃, carry out high-temperature calcination again, 1～10 ℃/min of heating rate, calcination time 5～20hr obtains the lithium-nickel-manganese-cobalt oxygen compound of secondary spherical structure after the cooling.
3. the lithium ion battery according to claim 2 preparation method of secondary ball nickel manganese oxygen plus plate material for lithium, it is characterized in that: described lithium salts is LiOHH2O, LiNO3 or Li2CO3.
4. lithium ion battery according to claim 2 is characterized in that with the preparation method of secondary ball nickel manganese oxygen plus plate material for lithium: described nickel salt, manganese salt and cobalt salt are a kind of in sulfate, nitrate and the chloride or two kinds.
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