CN109686970A - A kind of no cobalt richness lithium tertiary cathode material NMA and preparation method thereof - Google Patents
A kind of no cobalt richness lithium tertiary cathode material NMA and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of no cobalt richness lithium tertiary cathode material NMA and preparation method thereof.Its chemical formula is Li1+PNi1‑x‑y‑ zMnxAlyMzO2, in which: 0.03 < P <, 0.3,0.1 < X <, 0.6,0.01 < Y < 0.1,0.01 < Z < 0.3, M Ce3+、Ti4+、Zr4+、Mg2+One or more；Its presoma is nano-sheet agglomerated particles, 30-50 nanometers of the thickness of nano-sheet presoma.Main application and advantage of the present invention: replace value valuableness Co with cheap Mn, and by the way that excessive lithium (rich lithium) is added, by stratiform LiNiO2Phase and stratiform LiMnO2A kind of mutually compound NMA positive electrode for having prepared lithium-rich structure.Because being free of cobalt, preparation cost declines 20-30%；The positive electrode capacity reaches 190-200mAh/g, and 100 circulation volume conservation rates are 90-95%.
Description
Technical field
The present invention relates to field of lithium ion battery material preparation, and in particular to a kind of no cobalt richness lithium tertiary cathode material NMA
And preparation method thereof.
Background technique
With the high speed development of new energy, high-capacity lithium ion power battery becomes global new energy and produces and scientific and technological development
Hot spot.As the positive electrode for influencing lithium battery capacity key component, the emphasis of even more current research of technique, tertiary cathode material
NCA has many advantages, such as that capacity is big, voltage platform is high, is the high capacity positive electrode of new generation after tertiary cathode material NCM, is mesh
The new hot spot of preceding lithium battery research and development.With technological progress, under the premise of keeping high stability, raising tertiary cathode material (NCA,
NCM the content of nickel in) reduces expensive cobalt content, or even is free of cobalt, is the development side of current anode material of lithium battery
To all following such as from 333,532,622 (i.e. the Ni:Co:Mn=3:3:3, similarly hereinafter) of former NCM to the NCA811 researched and developed at present
The development path that nickel content gradually increases, cobalt content gradually decreases, greatly improve the capacity of tertiary cathode material, cost gradually
Decline.
However, nickel content gradually increases in presoma, cobalt content gradually decreases, the layer structure of tertiary cathode material can be made
Stability declines in charge and discharge process, and serious cationic mixing easily occurs, and makes the efficiency for charge-discharge, reversible of positive electrode
The stability of circulation is greatly reduced.The best NCA of performance is 811 at present, and the ratio between nickel and cobalt are 8:1 (molar ratio), cobalt content
Still higher, capacity is also difficult to more than 200mAh/g, this has become the technical bottleneck of tertiary cathode material NCA, becomes current
Tertiary cathode material key technical problem urgently to be resolved.
Layered lithium manganate LiMnO2It is a kind of high capacity positive electrode, theoretical charge/discharge capacity reaches 285mAh/g, and difference is not
It is mostly currently used lithium manganate having spinel structure LiMn2O42 times of positive electrode.But layered lithium manganate LiMnO2Structure is extremely unstable
Fixed, structure is easily collapsed in charge and discharge process, and is changed into the lower spinel-type LiMn of capacity2O4, make cyclical stability
Difference, this is also to be difficult to prepare stable layered lithium manganate LiMnO at present2The reason of.
It is well known that the capacity of lithium battery and the lithium content of positive electrode are closely related, theoretically, positive electrode can oneself
Higher by the lithium content deviate from, the lithium ion of deintercalation is more in charging, and capacity is higher, and therefore, rich lithium also becomes positive material
Material increases one of the means of capacity.But for nickel-base anode material NCA, rich lithium can only be attached to the table of material as lithia
Face not can enter material crystal structure, so not can increase its capacity not only, material basicity can be made to increase, and will reduce instead just
The cyclical stability of pole material, this is because the Li in positive electrode NCA+Content excessive (i.e. rich lithium) and air contact can give birth to
At lithium carbonate and lithium hydroxide, the abjection and insertion activity of Li ion are hindered significantly, declines its capacity and cyclical stability.
Summary of the invention
For deficiency present in background technique, technical problems to be solved are the present invention: providing a kind of high stability, low
Cost without cobalt richness lithium tertiary cathode material NMA (three kinds of elements of nickel manganese aluminium compound) and preparation method thereof.
The present invention is in order to solve the above technical problems, the technical solution used are as follows: a kind of no cobalt richness lithium tertiary cathode material
Expect that NMA, the chemical formula of the no cobalt richness lithium tertiary cathode material NMA are Li1+PNi1-x-y-zMnxAlyMzO2, presoma chemical formula
For Ni1-x-y-zMnxAlyMz(OH)2, in which: 0.03 < P <, 0.3,0.1 < X <, 0.6,0.01 < Y <, 0.1,0.01 < Z < 0.3,
M is Ce3+、Ti4+、Zr4+、Mg2+One or more；The presoma is nano-sheet agglomerated particles, the nano-sheet
30-50 nanometers of the thickness of presoma.
A kind of preparation method as described in claim 1 without cobalt richness lithium tertiary cathode material NMA, includes the following steps:
1) by soluble nickel salt, manganese salt, aluminium salt, cerium salt, titanium salt, zirconates, magnesium salts, according to the no cobalt richness lithium tertiary cathode
The corresponding stoichiometric ratio mixing of the required ingredient that the presoma chemical formula of material NMA determines；Deionized water is added, gold is made
Belong to salting liquid；
2) deionized water dissolving is added in precipitating reagent, is made into precipitant solution；
3) bottom water is added in precipitation reactor, the precipitating reagent that metal salt solution made from step 1), step 2) are made into
After each self-heating of solution, cocurrent is injected into precipitation reactor；Then it keeps the temperature, stir progress coprecipitation reaction, coprecipitation reaction
Terminate, filter while hot；Deionized water washing, vacuum drying treatment finally are carried out to the sediment filtered out, obtain the no cobalt
The presoma of rich lithium tertiary cathode material NMA；
4) presoma of the no cobalt richness lithium tertiary cathode material NMA is uniformly mixed with lithium source, is placed in oxygen atmosphere
Calcining, is ground up, sieved after then cooling to room temperature, and is made without cobalt richness lithium tertiary cathode material NMA.
Further, nickel salt described in the step 1) is one of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate or more
Kind；
The manganese salt is one of manganese nitrate, manganese acetate, manganese chloride and manganese sulfate or a variety of；
The aluminium salt is one of aluminum nitrate, aluminium chloride, aluminum sulfate and aluminum acetate or a variety of；
The cerium salt is one of cerous nitrate, cerous acetate, cerium chloride and cerous sulfate or a variety of；
The titanium salt is one of Titanium Nitrate, acetic acid titanium, cerous sulfate or a variety of；
The zirconates is one of zirconium nitrate, zirconium acetate, zirconium sulfate or a variety of；
The magnesium salts is one of magnesium nitrate, magnesium acetate, magnesium sulfate, magnesium chloride or a variety of；
In the metal salt solution, metal cation concentration is 0.01mol/L~2.0mol/L.
Further, precipitating reagent described in the step 2) is one or both of sodium hydroxide, potassium hydroxide；
Hydroxyl concentration is 0.1mol/L~10mol/L in the precipitant solution.
Further, bottom water additional amount in precipitation reactor described in the step 3), the 20-30% of Zhan Fanying total volume；
The coprecipitation reaction carries out under inert atmosphere protection, and reaction temperature is 40-90 DEG C, reaction time 1-3h, reaction system
PH value be 7-13.
Further, lithium source described in the step 4) is the one or two of lithium hydroxide, lithium carbonate, in additional amount
Lithium meets the mole of the required lithium of the no cobalt richness lithium tertiary cathode material NMA stoichiometric ratio.
Further, the presoma and lithium source are subjected to ball milling mixing in the step 4), in 350-700 degree preroast 2-
It 5 hours, takes out preroast product and is ground.
Further, the preroast product after the grinding is sintered in oxygen atmosphere furnace, sintering temperature 700-850
Degree, time are 15-30 hours.
Compared with prior art, the present invention beneficial effect is: (1) replacing valence with cheap Mn in NCA positive electrode
It is worth valuableness Co, and by the way that excessive lithium (rich lithium) is added, by stratiform LiNiO2Phase and stratiform LiMnO2It is mutually compound to have prepared a kind of richness
The NMA positive electrode of lithium layer structure, to achieve the purpose that improve capacity and stability, reduce cost.
(2) present invention, because being free of cobalt, is greatly reduced its preparation cost, under cost without cobalt richness lithium tertiary cathode material
Range of decrease degree reaches 20-30%.
(3) presoma Ni of the present invention without cobalt richness lithium tertiary cathode material1-x-y-zMnxAlyMz(OH)2For nano-sheet reunion
Particle has the characteristics that density is small, specific surface area is high, chemical reactivity is high, makes the anode formed in high-temperature burning process
Material layer structure is more perfect, and chemical property is more stable.
(4) different from existing ternary anode material precursor synthetic method, the presoma is using coprecipitation in height
Concentration, is added without complex ion NH at the low reaction time4 +Under the conditions of carry out, on the one hand, keep each precipitated cationic complete, rate of deposition >=
99.99%, remaining heavy metal ion content < 0.001g/l in filtrate substantially reduce the weight avoided in filtrate recovery processing
On the other hand metal ion pollution makes reaction efficiency greatly improve and (improve 200-300%), operating cost declines 40-50%.
(5) obtained without cobalt richness lithium tertiary cathode material, there is very high electro-chemical activity and cyclical stability, capacity
Reach 190-200mAh/g, 100 times circulation volume conservation rate reaches 90-95%.
Detailed description of the invention
Fig. 1 is presoma SEM figure of the present invention without cobalt richness lithium tertiary cathode material NMA；
Fig. 2 is SEM figure of the present invention without cobalt richness lithium tertiary cathode material NMA；
Fig. 3 is charge and discharge electrograph (the 100 circulations) curve graph of the present invention without cobalt richness lithium tertiary cathode material NMA.
Specific embodiment
Embodiments of the present invention are described in further detail with reference to the accompanying drawing.
As shown in Fig. 1 to Fig. 3, a kind of no cobalt richness lithium tertiary cathode material NMA, the no cobalt richness lithium tertiary cathode material
The chemical formula for expecting NMA is Li1+PNi1-x-y-zMnxAlyMzO2, presoma chemical formula is Ni1-x-y-zMnxAlyMz(OH)2, in which:
0.03 < P <, 0.3,0.1 < X <, 0.6,0.01 < Y < 0.1,0.01 < Z < 0.3, M Ce3+、Ti4+、Zr4+、Mg2+One kind
Or it is two or more；The presoma is nano-sheet agglomerated particles, and concrete shape is as shown in Figure 1, the nano-sheet presoma
30-50 nanometers of thickness.The presoma pattern of such no cobalt richness lithium tertiary cathode material NMA, structure have that density is small, compares table
The feature that area is high, chemical reactivity is high.The stratiform LiNiO that presoma is formed by high-temperature calcination2Phase and stratiform LiMnO2Phase
It is compound, a kind of NMA positive electrode of lithium-rich structure has been prepared, layer structure is more perfect, and chemical property is more stable,
Its capacity reaches 190-200mAh/g, and 100 times circulation volume conservation rate reaches 90-95%.
A kind of preparation method as described in claim 1 without cobalt richness lithium tertiary cathode material NMA, includes the following steps:
1) by soluble nickel salt, manganese salt, aluminium salt, cerium salt, titanium salt, zirconates, magnesium salts, according to the no cobalt richness lithium tertiary cathode
The corresponding stoichiometric ratio mixing of the required ingredient that the presoma chemical formula of material NMA determines；Deionized water is added, gold is made
Belong to salting liquid；It is namely Li according to the chemical formula of no cobalt richness lithium tertiary cathode material NMA1+PNi1-x-y-zMnxAlyMzO2, forerunner
Body chemical formula is Ni1-x-y-zMnxAlyMz(OH)2, in which: 0.03 < P <, 0.3,0.1 < X <, 0.6,0.01 < Y < 0.1,0.01
< Z < 0.3, M Ce3+、Ti4+、Zr4+、Mg2+One or more, have selected need produce preparation specific target before
Body is driven, X, Y, Z specific value determine that, Ce3+、Ti4+、Zr4+、Mg2+In the element species that specifically need to adulterate and rub accordingly
You amount also determine that, corresponding nickel salt, manganese salt, aluminium salt, cerium salt, titanium salt, zirconates, mole respectively required in magnesium salts are also
It has determined.
The nickel salt is one of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate or a variety of；
The manganese salt is one of manganese nitrate, manganese acetate, manganese chloride and manganese sulfate or a variety of；
The aluminium salt is one of aluminum nitrate, aluminium chloride, aluminum sulfate and aluminum acetate or a variety of；
The cerium salt is one of cerous nitrate, cerous acetate, cerium chloride and cerous sulfate or a variety of；
The titanium salt is one of Titanium Nitrate, acetic acid titanium, cerous sulfate or a variety of；
The zirconates is one of zirconium nitrate, zirconium acetate, zirconium sulfate or a variety of；
The magnesium salts is one of magnesium nitrate, magnesium acetate, magnesium sulfate, magnesium chloride or a variety of；
In metal salt solution made from reality, metal cation concentration is 0.01mol/L~2.0mol/L.
2) deionized water dissolving is added in precipitating reagent, is made into precipitant solution；The precipitating reagent is sodium hydroxide, hydroxide
One or both of potassium；Hydroxyl concentration is 0.1mol/L~10mol/L in the precipitant solution.
3) bottom water is added in precipitation reactor, the precipitating reagent that metal salt solution made from step 1), step 2) are made into
After each self-heating of solution, cocurrent is injected into precipitation reactor；Then it keeps the temperature, stir progress coprecipitation reaction, coprecipitation reaction
Terminate, filter while hot；Deionized water washing, vacuum drying treatment finally are carried out to the sediment filtered out, obtain the no cobalt
The presoma of rich lithium tertiary cathode material NMA；Bottom water additional amount in the precipitation reactor, the 20-30% of Zhan Fanying total volume
(volume ratio)；The coprecipitation reaction carries out under inert atmosphere protection, and reaction temperature is 40-90 DEG C, reaction time 1-3h,
The pH value of reaction system is 7-13.
4) presoma of the no cobalt richness lithium tertiary cathode material NMA is uniformly mixed with lithium source, is placed in oxygen atmosphere
Calcining, is ground up, sieved after then cooling to room temperature, and is made without cobalt richness lithium tertiary cathode material NMA.The lithium source is hydroxide
The one or two of lithium, lithium carbonate, the lithium in additional amount meet the no cobalt richness lithium tertiary cathode material NMA stoichiometric ratio
Required lithium mole.It is Li according to the chemical formula of no cobalt richness lithium tertiary cathode material NMA in actual production preparation process1+ PNi1-x-y-zMnxAlyMzO2, wherein 0.03 < P < 0.3, that is, lithium mole with the molar ratio of presoma at (1.03-1.3):
It is specifically chosen between 1, therefore the addition mole of lithium source also determines that.
The presoma and lithium source are subjected to ball milling mixing again, in 350-700 degree preroast 2-5 hours, take out preroast
Product is ground.Preroast product after the grinding is sintered in oxygen atmosphere furnace, sintering temperature is 700-850 degree,
Time is 15-30 hours.
Because being free of cobalt, it is greatly reduced its preparation cost, cost fall reaches 20-30%.Existed using coprecipitation
High concentration, is added without complex ion NH at the low reaction time4 +Under the conditions of carry out, on the one hand, keep each precipitated cationic complete, rate of deposition
>=99.99%, remaining heavy metal ion content < 0.001g/l in filtrate are substantially reduced and are avoided in filtrate recovery processing
On the other hand heavy metal ion pollution makes reaction efficiency greatly improve and (improve 200-300%), operating cost declines 40-50%.
Embodiment 1
LITHIUM BATTERY nickel sulfate hexahydrate 462.6g, LITHIUM BATTERY list water manganese sulfate 30.4g, LITHIUM BATTERY aluminum sulfate octadecahydrate 20g are taken,
Analytical pure sulfuric acid zirconium 1.1g is added deionized water, is configured to the solution of 1L, is scaled nickel sulfate, manganese sulfate, aluminum sulfate mixing water
Total concentration of metal ions is 2mol/l in solution, this is solution A；Analysis pure cerium hydroxide sodium 161.6g is taken, deionized water is added, matches
The solution of 1L is made, being scaled naoh concentration is 4mol/l, this is solution B.Bottom water (deionized water) is taken with 3L reactor
450ml, by A, B solution, cocurrent is pumped into 3L reactor progress coprecipitation reaction simultaneously, and reaction condition is: stirring intensity: in, charging
Time 30min, reaction time 2h, digestion time 60min, 60 DEG C of reaction temperature.Vacuum filter while hot, filter cake take out, and 1L is added
Deionized water, in 60 DEG C of agitator treating 30min, vacuum filter, filter cake is taken out, and 1L deionized water is added, in 60 DEG C of agitator treatings
30min, vacuum filter, filtrate save, and prepare nickel sulfate solution for next time.Filter cake takes out grinding, i.e., in 80 DEG C of drying 3h
For target positive electrode material precursor.The presoma is taken into 100g, is added LITHIUM BATTERY Lithium hydroxide monohydrate 50g, ground and mixed, then at
Preroast is carried out in tubular type oxygen atmosphere furnace, 350 DEG C of pre-calcination temperature, pre-firing times 2h, is taken out, is ground after the completion of preroast
Mill, is sintered in oxygen atmosphere furnace, and sintering temperature is 750 DEG C, sintering time 20h, takes out, grinds after the completion of sintering, sieve
Divide, as this target positive electrode, then carries out electrical property measurement.
Embodiment 2
LITHIUM BATTERY nickel sulfate hexahydrate 461.6g, LITHIUM BATTERY list water manganese sulfate 30.1g, LITHIUM BATTERY aluminum sulfate octadecahydrate 20g are taken,
Analytical pure sulfuric acid zirconium 0.7g, analytical pure sulfuric acid titanium 1.0g are added deionized water, are configured to the solution of 1L, are scaled nickel sulfate, sulphur
Sour manganese, aluminum sulfate, total concentration of metal ions is 2mol/l in zirconium sulfate mixed aqueous solution, this is solution A；Take analysis pure cerium hydroxide
Sodium 161.6g is added deionized water, is configured to the solution of 1L, and being scaled naoh concentration is 4mol/l, this is solution B.It will
A, cocurrent is pumped into 3L reactor progress coprecipitation reaction to B solution simultaneously, and reaction condition is: stirring intensity: in, feed time
30min, reaction time 2h, digestion time 60min, 60 DEG C of reaction temperature.Vacuum filter while hot, filter cake take out, be added 1L go from
Sub- water, in 60 DEG C of agitator treating 30min, vacuum filter, filter cake is taken out, and 1L deionized water is added, in 60 DEG C of agitator treatings
30min, vacuum filter, filtrate save, and prepare nickel sulfate solution for next time.Filter cake takes out grinding, i.e., in 80 DEG C of drying 3h
For target positive electrode material precursor.The presoma is taken into 100g, is added LITHIUM BATTERY Lithium hydroxide monohydrate 51g, ground and mixed, then at
Preroast is carried out in tubular type oxygen atmosphere furnace, 350 DEG C of pre-calcination temperature, pre-firing times 2h, is taken out, is ground after the completion of preroast
Mill, is sintered in oxygen atmosphere furnace, and sintering temperature is 780 DEG C, sintering time 20h, takes out after the completion of sintering, grinding, i.e.,
For this target positive electrode, electrical property measurement is then carried out.
Embodiment 3
LITHIUM BATTERY nickel sulfate hexahydrate 446.8g, LITHIUM BATTERY list water manganese sulfate 39.2g, LITHIUM BATTERY aluminum sulfate octadecahydrate 20g are taken,
Analytical pure sulfuric acid titanium 1.0g, analytical pure sulfuric acid cerium 1.6g are added deionized water, are configured to the solution of 1L, are scaled nickel sulfate, sulphur
Total concentration of metal ions is 2mol/l in sour manganese, aluminum sulfate mixed aqueous solution, this is solution A；Take analysis pure cerium hydroxide sodium
161.6g is added deionized water, is configured to the solution of 1L, and being scaled naoh concentration is 4mol/l, this is solution B.By A, B
Cocurrent is pumped into 3L reactor progress coprecipitation reaction to solution simultaneously, and reaction condition is: stirring intensity: in, feed time 30min,
Reaction time 2h, digestion time 60min, 60 DEG C of reaction temperature.Vacuum filter while hot, filter cake take out, and 1L deionized water is added, in
60 DEG C of agitator treating 30min, vacuum filter, filter cake take out, and 1L deionized water are added, in 60 DEG C of agitator treating 30min, vacuum mistake
Filter, filtrate save, and prepare nickel sulfate solution for next time.Filter cake takes out grinding, as target anode material in 80 DEG C of drying 3h
Material precursor.The presoma is taken into 100g, LITHIUM BATTERY Lithium hydroxide monohydrate 55g, ground and mixed, then at tubular type oxygen atmosphere is added
Preroast is carried out in furnace, 350 DEG C of pre-calcination temperature, pre-firing times 4h, is taken out after the completion of preroast, grinding, then at oxygen gas
It is sintered in atmosphere furnace, sintering temperature is 800 DEG C, sintering time 28h, is taken out after the completion of sintering, grinding, as this target anode material
Then material carries out electrical property measurement.
Embodiment 4
LITHIUM BATTERY nickel sulfate hexahydrate 452.1g, LITHIUM BATTERY list water manganese sulfate 32.8g, LITHIUM BATTERY aluminum sulfate octadecahydrate 24g are taken,
Analytical pure sulfuric acid zirconium 2.1g is added deionized water, is configured to the solution of 1L, is scaled nickel sulfate, manganese sulfate, aluminum sulfate mixing water
Total concentration of metal ions is 2mol/l in solution, this is solution A；Analysis pure cerium hydroxide sodium 161.6g is taken, deionized water is added, matches
The solution of 1L is made, being scaled naoh concentration is 4mol/l, this is solution B.By A, B solution, cocurrent is pumped into 3L reaction simultaneously
Device carries out coprecipitation reaction, and reaction condition is: stirring intensity: in, feed time 30min, reaction time 2h, digestion time
60min, 60 DEG C of reaction temperature.Vacuum filter while hot, filter cake take out, and 1L deionized water is added, in 60 DEG C of agitator treating 30min,
Vacuum filter, filter cake take out, and 1L deionized water is added, and in 60 DEG C of agitator treating 30min, vacuum filter, filtrate is saved, and is used for
Next time prepares nickel sulfate solution.Filter cake takes out grinding, as target positive electrode material precursor in 80 DEG C of drying 3h.By the forerunner
Body takes 100g, and LITHIUM BATTERY Lithium hydroxide monohydrate 56.4g is added, and ground and mixed carries out preroast in tubular type oxygen atmosphere furnace,
It 350 DEG C of pre-calcination temperature, pre-firing times 5h, is taken out after the completion of preroast, grinding is sintered in oxygen atmosphere furnace, is sintered
Temperature is 730 DEG C, and sintering time is for 24 hours, to take out after the completion of sintering, then grinding, as this target positive electrode carry out electrically
It can measurement.
Embodiment 5
LITHIUM BATTERY nickel sulfate hexahydrate 355.1g, LITHIUM BATTERY list water manganese sulfate 28.4g, LITHIUM BATTERY aluminum sulfate octadecahydrate 15g are taken,
Deionization is added in analytical pure sulfuric acid titanium 0.4g, analytical pure sulfuric acid zirconium 1.1g, analytical pure sulfuric acid cerium 0.6g, epsom salt 0.2
Water is configured to the solution of 1L, is scaled nickel sulfate, manganese sulfate, total concentration of metal ions is in aluminum sulfate mixed aqueous solution
1.5mol/l, this is solution A；Analysis pure cerium hydroxide sodium 121.2g is taken, deionized water is added, is configured to the solution of 1L, is scaled
Naoh concentration is 3mol/l, this is solution B.By A, B solution, cocurrent is pumped into 3L reactor progress coprecipitation reaction simultaneously, instead
Answering condition is: stirring intensity: in, feed time 30min, reaction time 2h, digestion time 60min, 60 DEG C of reaction temperature.While hot
Vacuum filter, filter cake take out, and 1L deionized water is added, and in 60 DEG C of agitator treating 30min, vacuum filter, filter cake is taken out, and 1L is added
Deionized water, in 60 DEG C of agitator treating 30min, vacuum filter, filtrate is saved, and prepares nickel sulfate solution for next time.Filter cake
In 80 DEG C of drying 3h, grinding, as target positive electrode material precursor are taken out.The presoma is taken into 100g, one water of LITHIUM BATTERY is added
Lithium hydroxide 42.3g, ground and mixed carry out preroast in tubular type oxygen atmosphere furnace, and 350 DEG C of pre-calcination temperature, preroast
Time 4h takes out after the completion of preroast, and grinding is sintered in oxygen atmosphere furnace, and sintering temperature is 800 DEG C, and sintering time is
30h, takes out after the completion of sintering, then grinding, as this target positive electrode carry out electrical property measurement.
Embodiment 6
Take LITHIUM BATTERY nickel sulfate hexahydrate 218.2g, LITHIUM BATTERY list water manganese sulfate 20.3g, LITHIUM BATTERY aluminum sulfate octadecahydrate
11.7g analyzes pure sour titanium 0.5g, analytical pure sulfuric acid zirconium 1.1g, deionized water is added, is configured to the solution of 1L, is scaled sulfuric acid
Nickel, manganese sulfate, total concentration of metal ions is 1mol/l in aluminum sulfate mixed aqueous solution, this is solution A；Take analysis pure cerium hydroxide sodium
80.8g is added deionized water, is configured to the solution of 1L, and being scaled naoh concentration is 2mol/l, this is solution B.By A, B
Cocurrent is pumped into 3L reactor progress coprecipitation reaction to solution simultaneously, and reaction condition is: stirring intensity: in, feed time 30min,
Reaction time 2h, digestion time 60min, 60 DEG C of reaction temperature.Vacuum filter while hot, filter cake take out, and 1L deionized water is added, in
60 DEG C of agitator treating 30min, vacuum filter, filter cake take out, and 1L deionized water are added, in 60 DEG C of agitator treating 30min, vacuum mistake
Filter, filtrate save, and prepare nickel sulfate solution for next time.Filter cake takes out grinding, as target anode material in 80 DEG C of drying 3h
Material precursor.The presoma is taken into 100g, LITHIUM BATTERY Lithium hydroxide monohydrate 28g, ground and mixed, then at tubular type oxygen atmosphere is added
Preroast is carried out in furnace, 500 DEG C of pre-calcination temperature, pre-firing times 4h, is taken out after the completion of preroast, grinding, then at oxygen gas
It is sintered in atmosphere furnace, sintering temperature is 800 DEG C, and sintering time is for 24 hours, to take out after the completion of sintering, grinding, as this target anode material
Then material carries out electrical property measurement.
Embodiment 7
LITHIUM BATTERY nickel sulfate hexahydrate 446.8g, LITHIUM BATTERY list water manganese sulfate 33.8g, LITHIUM BATTERY aluminum sulfate octadecahydrate 16g are taken,
Analytical pure sulfuric acid cerium 2.4g, analytical pure sulfuric acid zirconium 0.7g analyze pure epsom salt 9.9g, and deionized water is added, is configured to 1L
Solution, be scaled nickel sulfate, manganese sulfate, total concentration of metal ions is 2mol/l in aluminum sulfate mixed aqueous solution, this is solution
A；Analysis pure cerium hydroxide sodium 161.6g is taken, deionized water is added, is configured to the solution of 1L, being scaled naoh concentration is
4mol/l, this is solution B.By A, B solution, cocurrent is pumped into 3L reactor progress coprecipitation reaction simultaneously, and reaction condition is: stirring
Intensity: in, feed time 30min, reaction time 2h, digestion time 60min, 60 DEG C of reaction temperature.Vacuum filter while hot, filter cake
It takes out, 1L deionized water is added, in 60 DEG C of agitator treating 30min, vacuum filter, filter cake is taken out, and 1L deionized water is added, in 60
DEG C agitator treating 30min, vacuum filter, filtrate save, and prepare nickel sulfate solution for next time.Filter cake in 80 DEG C of drying 3h,
Take out grinding, as target positive electrode material precursor.The presoma is taken into 100g, LITHIUM BATTERY Lithium hydroxide monohydrate 56.4g is added,
Ground and mixed carries out preroast in tubular type oxygen atmosphere furnace, and 450 DEG C of pre-calcination temperature, pre-firing times 5h, prebake is burnt down
At rear taking-up, grinding is sintered in oxygen atmosphere furnace, and sintering temperature is 780 DEG C, sintering time 28h, is taken after the completion of sintering
Out, it grinds, as this target positive electrode, then carries out electrical property measurement.
Charge-discharge test:
Positive electrode prepared in embodiment is made into button cell, carries out electric performance test, data are as follows:
Basic electric property energy
| Title | Voltage platform | Charge-discharge magnification | Specific capacity mAh/g | 100 capacity retention ratio % |
| Embodiment 1 | 4.3V | 0.1C | 192 | >=93% |
| Embodiment 2 | 4.3V | 0.1C | 195 | >=90% |
| Embodiment 3 | 4.3V | 0.1C | 190 | >=92% |
| Embodiment 4 | 4.3V | 0.1C | 200 | >=90% |
| Embodiment 5 | 4.3V | 0.1C | 192 | >=94% |
| Embodiment 6 | 4.3V | 0.1C | 196 | >=96% |
| Embodiment 7 | 4.3V | 0.1C | 192 | >=95% |
After applying the present invention, replace value valuableness Co with cheap Mn, and by the way that excessive lithium (rich lithium) is added, by stratiform
LiNiO2Phase and stratiform LiMnO2A kind of mutually compound NMA positive electrode for having prepared lithium-rich structure.Because being free of cobalt, preparation
Cost declines 20-30%；The positive electrode capacity reaches 190-200mAh/g, and 100 circulation volume conservation rates are 90-
95%.
Claims (8)
1. a kind of no cobalt richness lithium tertiary cathode material NMA, it is characterised in that: the change of the no cobalt richness lithium tertiary cathode material NMA
Formula is Li1+PNi1-x-y-zMnxAlyMzO2, presoma chemical formula is Ni1-x-y-zMnxAlyMz(OH)2, in which: 0.03 < P <
0.3,0.1 < X <, 0.6,0.01 < Y < 0.1,0.01 < Z < 0.3, M Ce3+、Ti4+、Zr4+、Mg2+It is one or two kinds of with
On；The presoma is nano-sheet agglomerated particles, 30-50 nanometers of the thickness of the nano-sheet presoma.
2. a kind of preparation method as described in claim 1 without cobalt richness lithium tertiary cathode material NMA, it is characterised in that: including such as
Lower step:
1) by soluble nickel salt, manganese salt, aluminium salt, cerium salt, titanium salt, zirconates, magnesium salts, according to the no cobalt richness lithium tertiary cathode material
The corresponding stoichiometric ratio mixing of the required ingredient that the presoma chemical formula of NMA determines；Deionized water is added, metal salt is made
Solution；
2) deionized water dissolving is added in precipitating reagent, is made into precipitant solution；
3) bottom water is added in precipitation reactor, the precipitant solution that metal salt solution made from step 1), step 2 are made into
After each self-heating, cocurrent is injected into precipitation reactor；Then it keeps the temperature, stir and carry out coprecipitation reaction, coprecipitation reaction terminates,
It filters while hot；Deionized water washing, vacuum drying treatment finally are carried out to the sediment filtered out, obtain the no cobalt richness lithium three
The presoma of first positive electrode NMA；
4) presoma of the no cobalt richness lithium tertiary cathode material NMA is uniformly mixed with lithium source, is placed in oxygen atmosphere and calcines,
It is ground up, sieved, is made without cobalt richness lithium tertiary cathode material NMA after then cooling to room temperature.
3. the preparation method of no cobalt richness lithium tertiary cathode material NMA according to claim 2, it is characterised in that: the step
It is rapid 1) described in nickel salt be one of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate or a variety of；
The manganese salt is one of manganese nitrate, manganese acetate, manganese chloride and manganese sulfate or a variety of；
The aluminium salt is one of aluminum nitrate, aluminium chloride, aluminum sulfate and aluminum acetate or a variety of；
The cerium salt is one of cerous nitrate, cerous acetate, cerium chloride and cerous sulfate or a variety of；
The titanium salt is one of Titanium Nitrate, acetic acid titanium, cerous sulfate or a variety of；
The zirconates is one of zirconium nitrate, zirconium acetate, zirconium sulfate or a variety of；
The magnesium salts is one of magnesium nitrate, magnesium acetate, magnesium sulfate, magnesium chloride or a variety of；
In the metal salt solution, metal cation concentration is 0.01mol/L~2.0mol/L.
4. the preparation method of no cobalt richness lithium tertiary cathode material NMA according to claim 2, it is characterised in that: the step
It is rapid 2) described in precipitating reagent be one or both of sodium hydroxide, potassium hydroxide；
Hydroxyl concentration is 0.1mol/L~10mol/L in the precipitant solution.
5. the preparation method of no cobalt richness lithium tertiary cathode material NMA according to claim 2, it is characterised in that: the step
It is rapid 3) described in bottom water additional amount, the 20-30% of Zhan Fanying total volume in precipitation reactor；The coprecipitation reaction is in indifferent gas
Atmosphere protection is lower to be carried out, and reaction temperature is 40-90 DEG C, reaction time 1-3h, and the pH value of reaction system is 7-13.
6. the preparation method of no cobalt richness lithium tertiary cathode material NMA according to claim 2, it is characterised in that: the step
It is rapid 4) described in lithium source be lithium hydroxide, lithium carbonate one or two, the lithium in additional amount meets the no cobalt richness lithium three
The mole of the required lithium of first positive electrode NMA stoichiometric ratio.
7. the preparation method of no cobalt richness lithium tertiary cathode material NMA according to claim 2, it is characterised in that: the step
It is rapid 4) in the presoma and lithium source be subjected to ball milling mixing, in 350-700 degree preroast 2-5 hour, taking-up preroast product
It is ground.
8. the preparation method of no cobalt richness lithium tertiary cathode material NMA according to claim 7, it is characterised in that: will be described
Preroast product after grinding is sintered in oxygen atmosphere furnace, and sintering temperature is 700-850 degree, and the time is 15-30 hours.
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