CN108598457A - A kind of monocrystalline lithium-rich manganese-based anode material and preparation method thereof, lithium ion battery - Google Patents
A kind of monocrystalline lithium-rich manganese-based anode material and preparation method thereof, lithium ion battery Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of monocrystalline lithium-rich manganese-based anode material, during calcining lithium-rich manganese base material presoma prepares monocrystalline lithium-rich manganese-based anode material, including：S1:Pre-burning first is carried out to the lithium-rich manganese base material presoma, break process obtains the oxide for the lithium-rich manganese base material presoma broken up；S2:The oxide of the lithium-rich manganese base material presoma is sintered after mixing with lithium source, obtains the oxide of lithium-rich manganese base material presoma.It is highly preferred that being mixed into a small amount of additive while mixing lithium after pre-burning is broken, being mixed into additive can be merged with induced crystal growth and crystal boundary, advantageously form monocrystalline, improve the structure of crystal.And pre-burning is broken can reduce grain diameter to more satisfactory range, making to be sintered object has preferable dynamic performance, and more preferably mixture homogeneity is reached in mixed lithium and mixed additive, promotes the formation of monocrystalline.Preparation method whereby can get single crystallization degree height, the uniform lithium-rich manganese-based anode material of grain diameter.
Description
Technical field
The present invention relates to lithium battery material technical fields, and in particular to a kind of preparation side of monocrystalline lithium-rich manganese-based anode material
Method and application.
Background technology
There is higher energy density, higher operating voltage, good for the more other secondary cells of lithium ion battery
Cycle performance, advantages of environment protection are widely used in the fields such as Portable power source, energy storage base station, electric vehicle.Gently
The growth requirement of quantization and long continuation of the journey, urgent need is proposed to the raising of battery energy density.The capacity of positive electrode is
Most important one in many influence battery energy density factors, anode material for lithium-ion batteries commercially use at present includes
Cobalt acid lithium (LCO), ternary material (NCM, NCA), LiMn2O4 (LMO), LiFePO4 (LFP), their highest gram volumes are below
200mAh/g.And lithium-rich manganese-based anode material aLi2MnO3·(1-a)LiMO2【0<a<1, M=Ni, in Co, Mn, Al, V, Cr, Fe
It is one or more kinds of】, because with the alternative positive material for becoming next-generation lithium ion battery compared with high working voltage, high discharge capacity
One of material.There is maximum Railway Project in lithium-rich manganese-based anode material, head is imitated to be had in relatively low (about 75%), cyclic process now
The problem of apparent voltage and capacity attenuation.First charge discharge efficiency can pass through surface coating modification or special surface active at present
Technique is increased to 85% close to 90%.And voltage and the very fast problem of capacity attenuation are mainly due under high voltage in cyclic process
Cause material that broken agglomerate particle in parasitic electrochemistry side reaction and cyclic process, dusting and disengaging occurs with electrolyte
So that the reaction was continued and leads to the generations of other phases for fresh interior surface and the electrolyte of exposure, the evil of voltage and capacity is caused
Change.
This is because the lithium-rich manganese-based polynary positive pole material prepared at present, pattern is by hundreds of nanometers of primary particle group
Micron secondary spherical particle made of poly-, the low fastness of material structure mechanical strength of this secondary spherical granule-morphology is poor,
In the case of higher pressure reality, these secondary spherical particles will easily be compressed broken, lead to that material internal particle is exposed, side reaction increases
Phenomena such as summing it up digestion of metallic ion is aggravated, and chemical property declines.Primary particle grain size is excessively tiny simultaneously and fault of construction
More, easy recurring structure caves under high voltage charge and discharge, and second particle is difficult to including these excessively tiny particles coats,
Therefore the median surface side reaction of high voltage charge and discharge process is difficult to inhibit, and material structure is caused to destroy, secondary ball particle is also easy in addition
Lead to the safety problems such as flatulence.Therefore, it can effectively be solved by the high lithium-rich manganese-based anode material of preparation single crystallization degree above-mentioned
There are the problem of.
Chinese Patent Application No. 201510994882.2 discloses《A kind of system of the lithium-rich manganese-based polynary positive pole material of monocrystalline
Preparation Method》, this method use coprecipitation reaction method, prepare nickel and cobalt containing manganese magnesium-aluminum metal 0.2~4mol/L of ion concentration, precipitating reagent
Middle 0.2~4mol/L of carbon acid ion concentration, react pH7.0~9.0,30~70 DEG C of reaction temperature, ageing 4~for 24 hours after, separation
Sediment, dry the carbonate precursor under 100 DEG C of high temperature.The presoma is crushed into 0.2~4h of ball milling, and is mixed with lithium,
400~600 DEG C of 4~6h of calcining of first low temperature in oxygen-enriched atmosphere, then 950~1200 DEG C of 12~20h of calcining of high temperature, at the uniform velocity cool down cold
But, the higher (1.8~2.8g/cm of powder tap density is made3), cycle and the preferable monocrystalline of high rate performance it is lithium-rich manganese-based it is polynary just
Pole material.This method need to carry out in oxygen-enriched atmosphere, and production cost is higher, and during the calcining up to 16~26h, not to quilt
Calcined material does any broken equal interference, leads to still have a degree of aggregate phenomenon in high-temperature sintering process.Refer to figure
1, for the SEM figures of the lithium-rich manganese-based polynary positive pole material of monocrystalline prepared by the existing scheme, it is not difficult to find out material prepared by this method
Single crystallization degree is not high, obviously containing there are many fine graineds in Electronic Speculum shape appearance figure<The particle of 1um, these fine particles can also be with
More side reaction occurs for electrolyte, and left upper also has the structure that is adhered of class aggregate pattern (to be often referred to as in the industry in its figure
For class monocrystalline), grain diameter is also very uneven, these problems can all influence and cause the decaying of battery performance.
Invention content
The single crystallization of the lithium-rich manganese-based polynary positive pole material of monocrystalline prepared in view of aforementioned techniques is incomplete, grain size is uneven etc.
Problem, the present invention provide a kind of preparation method of monocrystalline lithium-rich manganese-based anode material, to be prepared single crystallization degree higher,
The better lithium-rich manganese-based anode material of granulation uniformity, to improve compacted density, cycle performance and the high rate performance of material.
In order to achieve the above object, the main technical schemes that the present invention uses include：
A kind of preparation method of monocrystalline lithium-rich manganese-based anode material prepares monocrystalline richness in calcining lithium-rich manganese base material presoma
During lithium manganese-based anode material, including：
Step S1:Pre-burning is carried out to the lithium-rich manganese base material presoma, break process obtains being broken up lithium-rich manganese-based
The oxide of material precursor；
Step S2:The oxide of the lithium-rich manganese base material presoma is mixed and is sintered with lithium source, is obtained described
Monocrystalline lithium-rich manganese-based anode material.
In a feasible embodiment of the invention, the condition of pre-burning described in step S1 is pre-burning 4- at 300-800 DEG C
10h.Preferably, calcined temperature is 300~500 DEG C, 500~600 DEG C or 600 DEG C~700 DEG C.Before lithium-rich manganese base material carbonate
Body is driven about to decompose at 450 DEG C or so.Preferably, burn-in time is 4h~8h or 8h~10h.
In a feasible embodiment of the invention, in step S1, after the break process, further comprise at sieving
Reason.The sieving is sieved using 200-300 mesh, and the smaller oxide of grain diameter can be obtained.
In a feasible embodiment of the invention, in step S2, the oxide and lithium of the lithium-rich manganese base material presoma
The mixing in source is uniformly mixed using in high mixer or ball mill.
In a feasible embodiment of the invention, sintering condition described in step S2 is to be sintered at 700-1100 DEG C
10-25h.Preferably, sintering temperature is 700~800 DEG C, 800~900 DEG C, 900~1000 DEG C or 1000 DEG C~1100 DEG C.It is excellent
Selection of land, sintering time are 10h~15h, 15h~20h or 20h~25h.
In a feasible embodiment of the invention, after the completion of sintering described in step S2, further comprise broken and mistake
Sieve processing.Broken sieving is sieved using 300~500 mesh, obtains the lithium-rich manganese-based anode material of monocrystalline pattern.Presoma after pre-burning
Oxide, hardness increases, it is not easy to be ground into fine slag by transition in broken.
In a feasible embodiment of the invention, the lithium-rich manganese base material presoma is hydroxide precursor
MnxCoyNi1-x-y(OH)2Or carbonate precursor MnxCoyNi1-x-yCO3, wherein 0 ＜ x≤1,0≤y ＜ 1, x+y≤1.
In a feasible embodiment of the invention, in step S2, further comprise before being sintered to the richness
Additive is added in the oxide and lithium source of lithium Mn-based material presoma；
Wherein, the additive is a kind of or more in the compound containing Mg, Al, Zr, Ti, Y, Si, La and B
Kind.
In a feasible embodiment of the invention, the additive is H3BO3Or B2O3；Or
The additive is H3BO3Or B2O3With one kind in the compound containing Mg, Al, Zr, Ti, Y, Si and La
Or a variety of mixture.
Preferably, the lithium source in the step S2 is the one or more of lithium acetate, lithium carbonate and lithium hydroxide, lithium source
The molecule molar ratio for the lithium-rich manganese-based anode material that addition is prepared as required is added, with the obtained lithium-rich manganese base material
The amount and lithium-rich manganese-based anode material general formula aLi of presoma2MnO3·(1-a)LiMO2The value of middle a is related.
In a feasible embodiment of the invention, the total amount of adding of the additive accounts for the lithium-rich manganese base material forerunner
The mass percent of oxide body is more than 0 and is less than or equal to 2%.
Preferably, the compound of the Mg is magnesia, magnesium hydroxide or magnesium carbonate.
Preferably, the compound of the Al is aluminium oxide, aluminium hydroxide, aluminum oxyhydroxide, aluminum fluoride, aluminum nitrate or phosphoric acid
Aluminium.
Preferably, the compound of the Zr is zirconium oxide.
Preferably, the compound of the Ti is titanium oxide.
Preferably, the compound of the Y is yttrium oxide or yttrium carbonate.
Preferably, the compound of the Si is silica.
Preferably, the compound of the La is lanthana.
The present invention also provides a kind of monocrystalline lithium-rich manganese-based anode materials, are prepared by any of the above-described embodiment；And
A kind of lithium ion battery, including the monocrystalline lithium-rich manganese-based anode material.
According to one embodiment of present invention, the lithium-rich manganese base material presoma is prepared via a method which to obtain：
Prepare mixing salt solution：According to lithium-rich manganese base material presoma MnxCoyNi1-x-y(OH)2Or MnxCoyNi1-x-yCO3
The molar ratio preparation soluble nickel salt of middle Mn, Co, Ni, the mixing salt solution of cobalt salt, manganese salt, wherein total concentration of metal ions is
0.1-3moL/L, wherein 0 ＜ x≤1,0≤y ＜ 1, x+y≤1；
It should be noted that in the specific implementation, presoma is not limited to above two, only both are most commonly seen
's.Lithium-rich manganese-based anode material is other than the lithium-rich manganese-based anode material containing lithium nickel cobalt manganese, it is also possible to can contain other metals, such as
Aluminium, vanadium, chromium or iron.Therefore, it is according to lithium-rich manganese-based anode material aLi to be prepared in the specific implementation2MnO3·(1-a)
LiMO2In species of metal ion in addition to lithium and molar ratio weigh corresponding metal salt；Wherein 0<a<1, M=Ni, Co,
It is one or more kinds of in Mn, Al, V, Cr, Fe.
Prepare aqueous slkali：Aqueous slkali is prepared, it is 0.1~5mol/L to make alkaline concentration；
Coprecipitation reaction：The mixing salt solution is mixed with the aqueous slkali, carries out coprecipitation reaction, reaction terminates to stir
6~36h of ageing is mixed, sediment is detached, is washed, is dried, smashes sieving, the lithium-rich manganese base material presoma is made.
Preferably, when preparing mixing salt solution, the solubility manganese salt is selected from manganese sulfate, manganese chloride, manganese nitrate, acetic acid
The combination of one or more of manganese, manganese oxalate and manganese citrate.Preferably, when preparing mixing salt solution, the soluble nickel
Salt is selected from the combination of one or more of nickel sulfate, nickel chloride, nickel nitrate, nickel acetate, nickel oxalate and citric acid nickel.It is preferred that
Ground, when preparing mixing salt solution, the soluble cobalt is selected from cobaltous sulfate, cobalt chloride, cobalt nitrate, cobalt acetate, cobalt oxalate and lemon
One or more of lemon acid cobalt combines.
Preferably, the soluble nickel salt that is used in preparing mixing salt solution, soluble manganese salt, soluble cobalt it is cloudy from
Son is preferably identical anion, such as selective chlorination nickel, manganese chloride, cobalt chloride.In coprecipitation reaction below, using phase
With anion salt can reduce ionic impurity, make that the soluble matter left in solution after coprecipitation reaction is more single, reduces sediment
Separating difficulty, while convenient for the recycling of soluble object in solution.
Preferably, when preparing aqueous slkali, it is additionally added ammonium hydroxide, preparation obtains the mixed solution of alkali and ammonium hydroxide, and alkali and ammonia
A concentration of 0.1~5mol/L of alkali in the mixed solution of water, ammonia concn are 0.1~5mol/L.Wherein ammonium hydroxide as complexing agent,
Several complexing of metal ion in mixing salt solution can be prevented metal ion by complexing agent to promote the progress of coprecipitation reaction
Precipitation there is apparent grade sequence, the co-precipitation effect being not achieved.
Preferably, the alkali is one or more of sodium hydroxide, sodium carbonate, potassium hydroxide and lithium hydroxide.
When selecting sodium carbonate, obtained sediment is lithium-rich manganese base material carbonate precursor.
Preferably, the mixing salt solution carries out in a kettle with the aqueous slkali, specifically：First add in a kettle
The deionized water for entering 25% volume ratio, under inert gas (argon gas, nitrogen etc.) protection, by mixing salt solution and aqueous slkali or
The mixed solution of alkali and ammonium hydroxide respectively while being evenly pumped into reaction kettle, controls the temperature 40 of reaction system in reaction kettle
~70 DEG C, pH value in reaction 9~12.5, speed of agitator, carry out coprecipitation reaction, continue after charging stirring ageing 6-36h, so
Sediment is filtered afterwards, wash, is dried, is broken up, 300~400 mesh is crossed and is sieved, the lithium-rich manganese base material is made
Presoma.PH value in reaction is controlled by adjusting mixing salt solution with the relative velocity of aqueous slkali or the mixed solution of alkali and ammonium hydroxide
System.
The beneficial effects of the invention are as follows：
(1) calcining step in the prior art is divided into two ranks by the present invention:Before i.e. first low temperature presintering lithium-rich manganese base material
4~10h of body is driven, so that it is oxidized to the oxide of lithium-rich manganese base material presoma under an oxygen-containing atmosphere, and its break process is obtained
The oxide of the lithium-rich manganese base material presoma smaller to grain size, then high temperature sintering is carried out, become smaller due to being sintered object grain size, because
This is more likely formed well-crystallized with better dynamic performance.And in the presoma for obtaining grain size smaller (0.3~6 micron)
Oxide mixed with lithium source, additive, can obtain preferably mixing spend, be also beneficial to additive play effect.
(2) present invention is added a certain amount of after low temperature presintering and the broken oxide obtained compared with the presoma of small particle
Additive, these additives or the fusing point that can reduce mixture, play the role of fluxing agent；Or reaction process can be changed
Dynamics, induced crystal growth and crystal boundary merge, improve the structure of crystal, advantageously form monocrystalline.It is obtained after pre-burning
Oxidation of precursor object, hardness increase, be not easy to be ground into fine slag by transition, relative to directly crushing presoma for, grain size is more
It is easily controlled in ideal range.
In fact, when preparing lithium-rich manganese-based anode material in the industry, the fine powder content in finished product is strictly controlled, fine powder is shape
Looks are irregular and particle of the grain size less than 0.5 micron, this particle are difficult removal in actual production and can be to positive electrodes
Using leaving prodigious security risk, and oxidation of precursor object hardness increases, and relative to carbonate precursor, can reduce harmful thin
The generation of powder.
(3) additive that the present invention uses is preferably boric acid (169 DEG C of fusing point) or boron oxide (450 DEG C of fusing point), is had non-
Often low fusing point, therefore after being mixed with solid material (oxide+lithium source of lithium-rich manganese base material presoma), boric acid and boron oxide
Become viscous liquid form at high temperature, be a kind of fluxing agent, reduce mixture fusing point, promotes crystal boundary to merge, favorably
In forming monocrystalline, the accounting of aggregate in product is reduced.Fluxing agent refers generally to that mixture softening, fusing or condensing temperature can be reduced
Substance, using fluxing agent can at high temperature from melting salt flux in grow crystal, need not by further increase sintering temperature
Crystal growth can be realized in degree, to reduce process costs and equipment requirement.
(4) present invention is handled in entire calcination stage by broken and sieving twice, is mixed after low temperature presintering
Before lithium, another time is before obtaining final product after high temperature sintering.It is crushed twice and sieving is handled, be conducive to final product list
Brilliant lithium-rich manganese-based anode material has uniform grain size.
The above technique effect, showing on battery performance has：Single crystallization degree is higher, and grain diameter is more uniform, pressure
Real density is bigger, and material is more closely knit, and the particle of high compacted density has higher mechanical strength, and it is steady can to improve crystal structure
It is qualitative, do not allow broken to cause crackle in pole piece nipping process.Single crystallization degree is higher, and positive electrode is made to have lower ratio
A large amount of fresh inner surface will not be exposed after surface area and failure, effectively reduces side reaction rate, slow down cyclic process electricity
The decaying of pressure.Single crystallization degree is higher, so that positive electrode is had more smooth surface, can preferably be contacted with conductive agent, drops
The impedance on low electrode surface.In short, the cycle performance that material prepared by the method for the present invention is applied to battery when battery is more preferable, battery
Internal resistance growth is slack-off, and voltage attenuation is slower.
Description of the drawings
Fig. 1 is the SEM figures of lithium-rich manganese-based polynary positive pole material made from Chinese patent application publication No. CN106920959A.
Fig. 2 is lithium-rich manganese-based anode material SEM figures prepared by the method for the present invention embodiment 2.
Fig. 3 is lithium-rich manganese-based anode material SEM figures prepared by the method for the present invention embodiment 1.
Fig. 4 is lithium-rich manganese-based anode material SEM figures prepared by comparative example 1.
Fig. 5 is that the mean voltage of the method for the present invention embodiment 2, embodiment 1 and comparative example 1 recycles comparison diagram.
Specific implementation mode
In order to preferably explain the present invention, in order to understand, below in conjunction with the accompanying drawings, by specific implementation mode, to this hair
It is bright to be described in detail.
In order to illustrate the present invention technique effect, design following concrete operations, prepare monocrystalline lithium-rich manganese-based anode material,
It characterizes microcosmic crystal morphology and is assembled into battery testing its performance.
One, prepared by presoma
(1) according to lithium-rich manganese base material presoma MnxCoyNi1-x-y(OH)2Or MnxCoyNi1-x-yCO3Middle Mn, Co, Ni's
The mixing salt solution of molar ratio preparation soluble nickel salt, cobalt salt, manganese salt, wherein total concentration of metal ions is 0.1-3moL/L,
Wherein 0 ＜ x≤1,0≤y ＜ 1, x+y≤1.
Or：
According to monocrystalline lithium-rich manganese base material aLi to be prepared2MnO3·(1-a)LiNibCocMndO2Middle Mn, Co, Ni's rubs
You are 0.1-3moL/L than preparation soluble nickel salt, the mixing salt solution of cobalt salt, manganese salt, total concentration of metal ions, it is preferable that
Wherein 0.2≤a≤0.8,0.3≤b≤0.8,0.1≤c≤0.4,0.1≤d≤0.4, b+c+d=1.Preferably, described solvable
Property nickel salt is one kind in nickel sulfate, nickel chloride, nickel nitrate and nickel acetate；Soluble manganese salt is manganese sulfate, manganese chloride, manganese nitrate
And one kind in manganese acetate；Soluble cobalt is one kind in cobaltous sulfate, cobalt chloride, cobalt nitrate and cobalt acetate.It is preferred that use
The soluble-salt of nickel cobalt manganese salt anion having the same.
Wherein, in the specific implementation, presoma is not limited to above two, and only both are most commonly seen.It is lithium-rich manganese-based just
Pole material is other than the lithium-rich manganese-based anode material containing lithium nickel cobalt manganese, it is also possible to can contain other metals, such as aluminium, vanadium, chromium or iron.
Then when preparing mixing salt solution, except aforementioned addition soluble nickel salt, soluble manganese salt, soluble cobalt, it is also possible to according to reality
Aluminum soluble salt, soluble vanadic salts, soluble chromic salts or solvable is added in the type of metal ion in the positive electrode to be prepared of border
Property molysite.Therefore, it is according to lithium-rich manganese-based anode material aLi to be prepared in the specific implementation2MnO3·(1-a)LiMO2In
Species of metal ion and molar ratio in addition to Li weigh corresponding metal salt；Wherein 0<a<1, M=Ni, Co, Mn, Al, V,
It is one or more kinds of in Cr, Fe.(2) mixed solution of aqueous slkali or alkali and ammonium hydroxide is prepared, alkaline concentration is 0.1~
5mol/L；A concentration of 0.1~5mol/L of alkali in the mixed solution of alkali and ammonium hydroxide, ammonia concn are 0.1~5mol/L；Wherein alkali
For one or more of sodium hydroxide, sodium carbonate, potassium hydroxide, lithium hydroxide.
(3) deionized water of 25% volume ratio of reaction kettle is added in a kettle, under inert gas protection, by step
(1) mixed solution for the aqueous slkali or alkali and ammonium hydroxide that nickel salt, cobalt salt, the mixing salt solution of manganese salt composition and step (2) is prepared
It is pumped into reaction kettle to uniformly continuous simultaneously respectively, controls 40~70 DEG C of the temperature of reaction system in reaction kettle, react pH, stir
Mix rotating speed carries out coprecipitation reaction, continues stirring ageing 6-36h after charging, is then filtered precipitated product, washes
It washs, dry, break up, then cross 300~400 mesh and sieved, to obtain lithium-rich manganese base material presoma.PH value in reaction is
It is controlled in pH9~12.5 by adjusting mixing salt solution with the relative velocity of aqueous slkali or the mixed solution of alkali and ammonium hydroxide.
Two, calcining lithium-rich manganese base material presoma prepares monocrystalline lithium-rich manganese-based anode material
(1) the lithium-rich manganese base material presoma of co-precipitation after pre-burning 4-10h, is crushed mistake after breaing up at 300-800 DEG C
200-300 mesh sieves to obtain the oxide of the smaller lithium-rich manganese base material presoma of grain diameter.
(2) oxide of above-mentioned lithium-rich manganese base material presoma is added with lithium source in high mixer or ball mill and is uniformly mixed
(or being uniformly mixed simultaneously with additive) re-sinters 10-25 hours at 700-1100 DEG C, excessively 300 after broken~
500 mesh sieve to obtain the lithium-rich manganese-based anode material of monocrystalline pattern.
Wherein, low temperature presintering and high temperature sintering correspond to two different chemical reaction processes respectively, and pre-burning corresponds to rich lithium manganese
The oxidation reaction of base material material precursor；The lithium-rich manganese base material presoma that high temperature sintering corresponds to after oxidation is reacted with lithium source,
Lithium-rich manganese-based anode material is made.
Wherein, the additive amount of additive is the 0- of the oxide mass for the lithium-rich manganese base material presoma for being mixed object
2wt%.Additive is Mg, Al, the compound of Zr, Ti, Y, Si, La, B element is one or more kinds of.Wherein it is preferred to which Mg is
Magnesia, magnesium hydroxide, magnesium carbonate；Al is aluminium oxide, aluminium hydroxide, aluminum oxyhydroxide, aluminum fluoride, aluminum nitrate, aluminum phosphate, Zr
For zirconium oxide, Ti is titanium oxide, and Y is yttrium oxide, yttrium carbonate, and Si is silica, and La is lanthana, and B is boric acid or boron oxide.Make
It uses boric acid or boron oxide as additive, has the function of fluxing agent, reduce mixture fusing point, promote crystal boundary to merge, have
Conducive to monocrystalline is formed, the accounting of aggregate in product is reduced.And other kinds of additive is mainly used for induced crystal growth
It is merged with crystal boundary, improves the structure of crystal, promote the formation of monocrystalline.Fluxing agent refers generally to that mixture softening can be reduced, melts
The substance of change or condensing temperature can grow crystal from melting salt flux at high temperature using fluxing agent
It is further preferable that the additive is H3BO3Or B2O3；Or the additive is H3BO3Or B2O3With selected from Mg,
The mixing of the compound one or more of Al, Zr, Ti, Y, Si and La.
Wherein, lithium source can be lithium acetate, it is lithium carbonate, one or two kinds of in lithium hydroxide, Li elements addition according to
" step 1 " aLi to be prepared2MnO3·(1-a)LiNibCocMndO2In a, b, c, d value and molecule with manganese cobalt nickel
After molar ratio calculates, the quality for weighing calculated value is added.
It is specific embodiment below
Embodiment 1
1. by the molar ratio 4 of Mn, Co, Ni：1：1 prepares the mixing salt solution of nickel sulfate, cobaltous sulfate, sulfuric acid manganese salt, always
Concentration of metal ions is 2moL/L.
2. preparing the mixed solution of sodium hydroxide and ammonium hydroxide, a concentration of 2mol/L of sodium hydroxide, ammonia concn 3mol/
L。
3. adding the deionized water of 25% volume ratio of reaction kettle into reaction kettle, by hydrogen-oxygen under the inert atmosphere protections such as nitrogen
The mixed solution for changing sodium and ammonium hydroxide is passed through in reaction kettle, and control metal salt solution is 0.5L/h into flow quantity, adjusts sodium hydroxide
System pH is made to maintain 10.2 with the flow of ammonium hydroxide mixed solution, process control reaction temperature is 55 degree, and mixing speed is
600rpm/min continues stirring ageing 10h, is then filtered precipitated product, washs, dries, cross 400 mesh after charging
It is sieved to obtain lithium-rich manganese base material presoma Ni1/6Co1/6Mn2/3(OH)2。
4. walking and not being mixed into additive, operation is as follows：
At 520 DEG C after pre-burning 8h, cooling is crushed and breaks up 3. lithium-rich manganese base material presoma that step is co-precipitated
300 mesh sieve is crossed afterwards, and sieve obtains the oxide of the lithium-rich manganese base material presoma of grain diameter smaller (about 0.3um-6um), then will
(molar ratio Li/Me=1.2/0.8, Me are metal ion in mixing salt solution to the oxide and 71.4g lithium carbonates of 100g presomas
Mole sum total) after mixing, be sintered 12h hour at 920 DEG C in high mixer, 400 mesh of mistake sieve after broken, obtain not complete
The 0.5Li of full single crystallization2MnO3·0.5LiNi1/3Co1/3Mn1/3O2Lithium-rich manganese-based anode material.Using electron microscope observation,
Its grain shape is shown in the SEM figures of Fig. 3.
By Fig. 3, it can be seen that, lithium-rich manganese-based anode material manufactured in the present embodiment is in incomplete single crystallization pattern, particle
Diameter size is not uneven enough, and maximum larger with the grain size difference of smallest particles, there is also the class monocrystalline for being adhered state on a small quantity in the upper right corner
Pattern, only portion of monocrystalline.It can be seen that have pre-burning broken but not additivated calcine technology is made it is lithium-rich manganese-based just
Pole material, is only capable of portion of monocrystalline, and there are still aggregates, are moderate aggregate pattern.Fig. 3 is compared with Fig. 1, this implementation
Example can obtain the lithium-rich manganese-based anode material of pattern close with the prior art representated by Fig. 1, while compared to Figure 1 compared with this
Embodiment obtains lithium-rich manganese-based anode material SEM figures and has no the irregular fine slag of apparent small particle or fine powder.
Embodiment 2
1. by the molar ratio 4 of Mn, Co, Ni：1：1 prepares the mixing salt solution of nickel sulfate, cobaltous sulfate, sulfuric acid manganese salt, always
Concentration of metal ions is 2moL/L.
2. preparing the mixed solution of sodium hydroxide and ammonium hydroxide, a concentration of 2mol/L of sodium hydroxide, ammonia concn 3mol/
L。
3. adding the deionized water of 25% volume ratio of reaction kettle into reaction kettle, by hydrogen-oxygen under the inert atmosphere protections such as nitrogen
The mixed solution for changing sodium and ammonium hydroxide is passed through in reaction kettle, and control metal salt solution is 0.5L/h into flow quantity, adjusts sodium hydroxide
System pH is made to maintain 10.2 with the flow of ammonium hydroxide mixed solution, process control reaction temperature is 55 degree, and mixing speed is
600rpm/min continues stirring ageing 10h, is then filtered precipitated product, washs, dries, cross 400 mesh after charging
It is sieved to obtain lithium-rich manganese base material presoma Ni1/6Co1/6Mn2/3(OH)2。
4. 3. presoma that step is co-precipitated at 520 DEG C after pre-burning 10h, it is cooling, broken break up after cross 300 mesh
Sieve obtains the oxide of the lithium-rich manganese base material presoma of grain diameter smaller (about 0.3um-6um), then by 100g presomas
Oxide, 0.2g nano zircites, 0.1gH3BO3(molar ratio Li/Me=1.2/0.8, Me are that salt-mixture is molten with 71.4g lithium carbonates
Mole sum total of metal ion in liquid) it after mixing, is sintered 12h hours at 920 DEG C in high mixer, 400 are crossed after broken
Mesh sieves, and the 0.5Li of monocrystalline pattern is made2MnO3·0.5LiNi1/3Co1/3Mn1/3O2Lithium-rich manganese-based anode material, using electronic display
Micro mirror is observed, and grain shape is shown in the SEM figures of Fig. 2.By Fig. 2 it can be seen that, lithium-rich manganese-based anode material manufactured in the present embodiment,
Whole single crystallizations and the appearance of soilless sticking body, are presented good monocrystalline pattern, and granular size is well-balanced, surface is smooth.
Therefore, the broken formation for helping somewhat to monocrystalline pattern of pre-burning, but compared with Example 2, embodiment 2
Lithium-rich manganese-based anode material, which has, made from " pre-burning is crushed+special additive cofiring " becomes apparent and good monocrystalline pattern.
Compaction data in table 1 also indicates that single crystallization degree is higher, and compacted density is higher, and material is more closely knit.
By embodiment 2 compared with Example 1 compared with it is found that embodiment 1 is crushed through pre-burning but does not introduce the system of additive cofiring
The lithium-rich manganese-based anode material that standby technique obtains is not so good as embodiment 2, but can be lithium-rich manganese-based with prior art preparation shown in Fig. 1
The pattern of positive electrode is suitable, and has less irregular fine slag or fine powder.
Embodiment 3
4. the present embodiment and the difference of embodiment 2 only walk that mixed additive is different, and additive is titanium oxide and oxygen the
Change boron, operation is as follows：3. presoma that step is co-precipitated at 520 DEG C after pre-burning 8h, it is cooling, broken break up after mistake
300 mesh sieve to obtain the oxide of the lithium-rich manganese base material presoma of grain diameter smaller (about 0.3um-6um), then by 100g forerunner
The oxide of body, the nano-TiO of 0.5g2、0.2g B2O3(molar ratio Li/Me=1.2/0.8, Me are mixing with 71.4g lithium carbonates
Mole sum total of metal ion in salting liquid) it after mixing, is sintered 12h hours at 920 DEG C in high mixer, the mistake after broken
400 mesh sieve, and the 0.5Li of monocrystalline pattern is made2MnO3·0.5LiNi1/3Co1/3Mn1/3O2Lithium-rich manganese-based anode material, using electronics
Micro- sem observation, grain shape are very close with Fig. 2.
Embodiment 4
4. the present embodiment and the difference of embodiment 2 only walk mixed additive the different, additive only simple addition boron
Acid, but additive amount is increased, operation is as follows：3. presoma that step is co-precipitated is cooling, broken at 520 DEG C after pre-burning 8h
It is broken break up after cross 300 mesh sieve to obtain the oxide of the lithium-rich manganese base material presoma of grain diameter smaller (about 0.3um-6um), then
By the oxide of 100g presomas, the H of 0.8g3BO3(molar ratio Li/Me=1.2/0.8, Me are salt-mixture with 71.4g lithium carbonates
Mole sum total of metal ion in solution) it after mixing, is sintered 12h hours at 920 DEG C in high mixer, the mistake after broken
400 mesh sieve, and the 0.5Li of monocrystalline pattern is made2MnO3·0.5LiNi1/3Co1/3Mn1/3O2Lithium-rich manganese-based anode material, using electronics
Micro- sem observation, the consistent appearance that grain shape is presented with Fig. 2.
Embodiment 5
4. the present embodiment and the difference of embodiment 2 only walk that mixed additive is different, and additive is zirconium oxide and oxygen the
Change aluminium, operation is as follows：3. presoma that step is co-precipitated at 520 DEG C after pre-burning 4h, it is cooling, broken break up after mistake
300 mesh sieve to obtain the oxide of the lithium-rich manganese base material presoma of grain diameter smaller (about 0.3um-6um), then by 100g forerunner
The oxide of body, the ZrO of 0.4g2, 0.2g Al2O3, (molar ratio Li/Me=1.2/0.8, Me are salt-mixture to 71.4g lithium carbonates
Mole sum total of metal ion in solution) in high mixer after mixing, 20h is sintered at 1050 DEG C, 400 mesh are crossed after crushing
The 0.5Li of monocrystalline pattern is made in sieve2MnO3·0.5LiNi1/3Co1/3Mn1/3O2Lithium-rich manganese-based anode material, using electron microscopic
Sem observation, the consistent appearance that grain shape is presented with Fig. 2.
Comparative example 1
Comparative example the difference from example 2 is that, it is both broken without pre-burning in 4. calcination process that this comparative example is walked the
Operation, while being also not added with any additive, operation is as follows：
3. 100g steps are co-precipitated to lithium carbonate (the molar ratio Li/Me of lithium-rich manganese base material presoma and 61.4g obtained
=1.2/0.8, Me are mole sum total of metal ion in mixing salt solution) it after mixing, is sintered at 920 DEG C in high mixer
12h hours, 400 mesh excessively sieved to obtain the 0.5Li of aggregate after broken2MnO3·0.5LiNi1/3Co1/3Mn1/3O2It is lithium-rich manganese-based
Positive electrode.Using electron microscope observation, grain shape is shown in the SEM figures of Fig. 4.Fig. 4 is both to be crushed without pre-burning or do not attach
Aggregate pattern is presented in the lithium-rich manganese-based anode material for adding the Conventional calcination technique of agent to prepare completely, and no monocrystalline occurs, grain size compared with
Greatly, suitable with presoma, rough, large specific surface area.
It is test case below
The lithium-rich manganese-based anode material that embodiment 2, embodiment 1 and comparative example 1 are obtained, respectively with conductive agent Super, viscous
It is 9 that agent PVDF, which is tied, according to mass ratio：0.5：0.5 is prepared by mixing into slurry, and electricity is prepared by processes such as coating, drying, rolling
Pole, and it is assembled into battery together with graphite electrode, diaphragm, electrolyte.Electrolyte is to contain ethylene carbonate ester solvent and hexafluoro phosphorus
The common lithium-ion battery electrolytes of sour lithium.Embodiment 2 and embodiment 1, the cycle conservation rate of comparative example 1 and internal resistance variation are seen below
Table.
Table 1
It can see in table 1, between the monocrystalline lithium-rich manganese-based anode material that embodiment 2 obtains and its surface and conductive agent
Electrical contact it is more preferable.For the first time activate after 83 Ω of internal resistance, cycle 100 times after, 2 internal resistance of embodiment rises to 224 Ω, hence it is evident that be less than pair
The internal resistance of the lithium-rich manganese base material battery of the aggregate pattern of ratio 1；Embodiment 1 is the rich lithium of moderate aggregate pattern
Manganese-based anode material, internal resistance is also more lithium-rich manganese-based than the aggregate pattern of comparative example 1 after activating internal resistance for the first time and recycling 100 times
The internal resistance of material cell is small.
Therefore, in provable lithium-rich manganese-based anode material aggregate that there are ratios is directly related with internal resistance, aggregate is got over
More, internal resistance is bigger.The monocrystalline lithium-rich manganese-based anode material that embodiment 2 obtains, due to almost all single crystallization, grain diameter is very
Uniformly, therefore compacted density can reach 3.72g/cm3, hence it is evident that it is higher than comparative example 1, and compacted density (1.8 compared with the existing technology
~2.8g/cm3) it is higher by nearly 2 times.In addition, after being recycled 100 times under the 0.2C charge-discharge magnifications of embodiment 2, capacity retention ratio may be used also
Up to 90.2%, the conservation rate 82.6% compared to comparative example 1 can be 8 percentage points high.
As shown in figure 5, the mean voltage for embodiment 2 and embodiment 1, comparative example 1 recycles comparison diagram, recycled at 25 DEG C
Mean voltage, 2.0~4.6V, 0.2C/0.2C, wherein 2 mean voltage curve of embodiment are the most steady.
The test result of complex chart 5 and table 1 can obtain, although the monocrystalline pattern that embodiment 2 obtains is lithium-rich manganese-based
Initial discharge capacity and mean voltage want low compared with the lithium-rich manganese-based anode material of 1 aggregate pattern of embodiment 1 and comparative example
Some, but the cycle performance of embodiment 2 is more preferable, voltage attenuation is slower, and capacity retention ratio is higher.And pre-burning in calcine technology
Broken but not additivated embodiment 1, the lithium-rich manganese-based anode material of obtained moderate aggregate pattern, various aspects
Performance is interposed between the two.When demonstrating again that driving body before calcination prepares lithium-rich manganese-based anode material as a result, pass through pre-burning
Broken mixed lithium and the operation for introducing additive cofiring, each contribute to the formation of lithium-rich manganese-based anode material monocrystalline pattern, have
The significantly technique effect of optimization lithium-rich manganese base material chemical property.Lithium-rich manganese base material oxidation of precursor is wherein obtained after pre-burning
Object, oxide hardness is larger, is not easy to be ground into harmful fine powder or fine slag, and the lithium-rich manganese base material presoma after grinding
Oxide has the specific surface area of bigger and inhales the reactivity of lithium, and higher additive mixture homogeneity can reduce reaction
Condition requires and equipment requirement, and additive is enable to play one's part to the full when compared with few additive, and monocrystalline is finally prepared
The high lithium-rich manganese-based anode material of change degree.
Claims (10)
1. a kind of preparation method of monocrystalline lithium-rich manganese-based anode material, which is characterized in that in calcining lithium-rich manganese base material presoma
Include during preparing monocrystalline lithium-rich manganese-based anode material：
Step S1:Pre-burning is carried out to the lithium-rich manganese base material presoma, break process obtains the lithium-rich manganese base material broken up
The oxide of presoma；
Step S2:The oxide of the lithium-rich manganese base material presoma is mixed and is sintered with lithium source, the monocrystalline is obtained
Lithium-rich manganese-based anode material.
2. preparation method according to claim 1, which is characterized in that in step sl, the temperature of the pre-burning is 300-
800 DEG C, time 4-10h.
3. preparation method according to claim 1, which is characterized in that in step sl, after the break process, into one
Step includes sieving processing.
4. preparation method according to claim 1, which is characterized in that in step s 2, the temperature of the sintering is 700-
1100 DEG C, time 10-25h.
5. preparation method according to claim 1, which is characterized in that in step s 2, after sintering, further comprise brokenly
Broken and sieving processing.
6. according to claim 1-5 any one of them preparation methods, which is characterized in that in step s 2, before sintering into
One step includes that additive is added into the oxide of the lithium-rich manganese base material presoma and lithium source；Wherein, the additive choosing
From one or more of the compound containing Mg, Al, Zr, Ti, Y, Si, La and B.
7. preparation method according to claim 6, which is characterized in that
The additive is H3BO3Or B2O3；Or
The additive is H3BO3Or B2O3With it is a kind of or more in the compound containing Mg, Al, Zr, Ti, Y, Si and La
The mixture of kind.
8. preparation method according to claim 7, which is characterized in that the total amount of adding of the additive accounts for the rich lithium manganese
The mass percent of sill oxidation of precursor object is more than 0 and is less than or equal to 2%.
9. a kind of monocrystalline lithium-rich manganese-based anode material obtained according to any one of claim 1~8 preparation method.
10. a kind of lithium ion battery, which is characterized in that include the monocrystalline lithium-rich manganese-based anode material described in claim 9.
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Effective date of registration: 20190702 Address after: 101102 Beijing Tongzhou District Huanyu Road No.3 Building No.14, 3 Floors Applicant after: Sander New Energy Technology Development Co., Ltd. Applicant after: Thornton Amperex Technology Limited Address before: Unit 402, Fuqing Huayuan Commercial and Residential Building, Bayi Town, Linzhi City, Tibet Autonomous Region Applicant before: Sound Group Co.,Ltd. Applicant before: Thornton Amperex Technology Limited |
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Application publication date: 20180928 |