CN103280570A - Preparation method of micron-order single-crystal nickel lithium manganate anode material - Google Patents
Preparation method of micron-order single-crystal nickel lithium manganate anode material Download PDFInfo
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Abstract
The invention discloses a preparation method of a micron-order single-crystal nickel lithium manganate anode material. The preparation method comprises the following steps of: preparing a nickel-manganese composite hydroxide in a solution, and oxidizing the nickel oxide manganese hydroxide so as to obtain composite compound seed crystal; mixing and reacting nickel salts, manganese salts and alkali compounds in a solution, at the same time, oxidizing so as to grow the composite compound seed crystal till the particle size is 0.1-30 micrometers; directly mixing the obtained crystal particles with a lithium compound in a solution, or mixing the crystal particles which is subjected to acid treatment with the lithium compound, subsequently carrying out an oxidation reaction in an oxidability environment, filtering and drying, and roasting the precursor of the nickel lithium manganate compound so as to obtain the micron-order single-crystal nickel lithium manganate anode material. By utilizing the preparation method, the diameters and the shapes of the single crystal particles can be controlled, and the obtained anode material is of a micron-order single-crystal structure, has a large and uniform particle diameter, is small in lattice imperfection and uniform in composition, and has high energy density, good structural stability and good circulation performance.
Description
Technical field
The present invention relates to the positive electrode field of lithium rechargeable battery, relate in particular to a kind of preparation method of micron order monocrystalline nickel manganate cathode material for lithium.
Background technology
Along with the progress of science and technology and the raising of living standards of the people, environmental pollution, fossil fuel resource is in short supply etc., and problem seems serious day by day, and the development new-energy automobile is considered to address these problems one of effective method.Yet as the core key technology of electric automobile, big the universal of electric automobile that limited of the development pole of power battery technology.Electrokinetic cell requires to have high security, high-energy and high power density, remarkable cycle life and high power charging-discharging, environmental friendliness, characteristics such as cost and price is moderate.And lithium secondary battery has extended cycle life because of the energy density height, is easy to advantages such as design, is widely regarded as follow-on electrokinetic cell.Along with improving constantly of cell making process and charge power supply technology, take into account the requirement of high-energy-density and high-power power lithium secondary battery, the exploitation of positive electrode is particularly crucial.A new generation's positive electrode material of lithium secondary cell is paid close attention to greatly and is developed.As lithium nickelate (LiNiO
2) material, ternary system nickle cobalt lithium manganate (LiCo
xNi
yMn
zO
2) material, LiFePO 4 (LiFePO
4) material, spinel lithium manganate (LiMn
2O
4) material and the high-potential material of charge and discharge platform more than 4.5V etc. just becoming typical case's representative of lithium secondary battery New-type electric machine material.
At spinel lithium manganate (LiMn
2O
4) the spinelle nickel LiMn2O4 (LiNi that grows up on the material foundation
0.5Mn
1.5O
4), with LiMn2O4 (LiMn
2O
4) equally be the positive electrode with three-dimensional lithium ion passage, reversible capacity is 146.7mAh/g, similar with LiMn2O4, but its actual capacity can reach more than 90% of theoretical capacity.And its voltage platform is about 4.7V, corresponding to Ni
2+/ Ni
4+Oxidation-reduction process, can eliminate corresponding to Mn substantially
3+/ Mn
4+The 4V platform of oxidation-reduction process, will exceed more than 15% than the 4V voltage platform of LiMn2O4, and the cyclical stability under the high temperature also had the lifting of matter than original LiMn2O4, be the first-selected positive electrode of high-power lithium secondary battery.Through development in recent years, the especially development of high potential electrolyte and barrier film, high potential nickel LiMn2O4 moves towards the practicability exploitation from technology of preparing, basic Electrochemical Properties etc. gradually.For example, " nickel LiMn2O4-graphite " battery of Japanese NEC assembling also has the capability retention more than 80% after 1C circulation 500 times; " nickel LiMn2O4-lithium titanate " battery of the Ohzuku of Osaka, Japan City University and SANYO cooperation assembling also has 90% capability retention after 2C circulation 2000 times; Korea S's LG chemistry has been manufactured experimently 600mAh's " nickel LiMn2O4-graphite " soft-package battery unit.But circulation and the poor storage performance of this material under high temperature (more than 55 ℃) therefore, is that the lithium ion battery of positive electrode active materials exists shortcomings such as serious self-discharge phenomenon and reversible capacity decay be too fast with the nickel LiMn2O4.But guarantee the actual specific capacity of nickel manganate cathode material for lithium and improve high temperature circulation that material that must the development of new structure or current material carried out modification is with the chemical property of raising material.
According to discovering: increase the bulk density that single crystal grain diameter (being the single crystal grain size) can not only improve powder, and be convenient to coating and electrode processing etc., the nickel LiMn2O4 of bulky grain diameter has excellent high low temperature cycle performance, and the polarization of electrode internal resistance is less.
At present, the nickel LiMn2O4 that is obtained by traditional wet method only has little particle diameter, even and it is calcined to carry out particle grow up, the bulky grain that can not obtain to wish.Though and the solid phase method process is simple, easy volume production, synthetic material granule is big, and homogeneity is poor, the energy consumption height.And for synthetic multicomponent material, reactant mixes inhomogeneous, and the material component nonstoichiometry forms dephasign easily, has had a strong impact on the cycle performance of material.Therefore, control single crystal grain diameter and grain shape obtain the few nickel LiMn2O4 of uniform lattice defect and seem particularly necessary.
Summary of the invention
The preparation method that technical problem solved by the invention has been to overcome existing nickel manganate cathode material for lithium is difficult to make the micron order monocrystalline, perhaps preparation method's energy consumption is high and crystal homogeneity that make is poor, the crystal that perhaps makes is formed nonstoichiometry, dephasign is many, defectives such as cycle performance difference provide a kind of preparation method of micron order monocrystalline nickel manganate cathode material for lithium.Preparation method of the present invention can control diameter and the shape of single crystal grain, the positive electrode that obtains has the micron order mono-crystalline structures, have bigger, uniform particle diameter, lattice defect is few and form even, make the positive electrode that makes not only have very high bulk density, also have high-energy-density, structural stability is good, have good cycle performance, its high-temperature behavior is compared with common nickel lithium manganate material and is greatly improved.
The present invention solves the problems of the technologies described above by the following technical programs.
The invention provides a kind of preparation method of micron order monocrystalline nickel manganate cathode material for lithium, it comprises the steps:
(1) be that the ratio of 2.9:1～3.2:1 makes nickel-manganese composite hydroxide in solution in the mol ratio of Mn:Ni, the described nickel-manganese composite hydroxide of oxidation gets the complex chemical compound seed crystal;
(2) under the situation that described complex chemical compound seed crystal exists, in the mol ratio of Mn:Ni be the ratio of 2.9:1～3.2:1 in solution with nickel salt, manganese salt and alkali compounds hybrid reaction, and carry out oxidation simultaneously, make described complex chemical compound seed crystal grow up to particle diameter be 0.1～30 micron, get crystal grain;
(3) be that the ratio of 3:1.8～3:2.3 is mixed in solution with described crystal grain and lithiumation thing in the mol ratio of Mn:Li, carry out oxidation reaction in oxidative environment, it is dry to filter the back, gets the presoma of nickel LiMn2O4 compound;
Perhaps, with the described crystal grain of acid treatment, get the crystal grain that proton replaces, the crystal grain that described proton is replaced and lithiumation thing are the ratio mixing of 3:1.8～3:2.3 in the mol ratio of Mn:Li then, in oxidative environment, carry out oxidation reaction, it is dry to filter the back, gets the presoma of nickel LiMn2O4 compound;
(4) presoma with described nickel LiMn2O4 compound carries out roasting, namely.
In the step (1), the preparation method of described nickel-manganese composite hydroxide and condition can be conventional method and the condition of using in this area.Among the present invention, the preparation method of described nickel-manganese composite hydroxide preferably adopts following manner to carry out: under anaerobic voltinism environment, in water nickel salt and manganese salt are mixed, with the alkali compounds reaction, get final product.Wherein, described nickel salt can be the conventional nickel salt that uses in this area, preferably is in nickelous sulfate, nickel nitrate, nickel chloride and the nickel acetate one or more; Described manganese salt can be the conventional manganese salt that uses in this area, preferably is in manganese sulfate, manganese nitrate, manganese chloride and the manganese acetate one or more; Described alkali compounds is the conventional alkali compounds that uses in this area, preferably is in KOH, NaOH, LiOH and the ammoniacal liquor one or more, more preferably is NaOH; The solvent of described solution is the conventional solvent that uses in this area, is generally water.When described anaerobic voltinism environment referred to that described reaction is carried out, oxygen-free voltinism component in the system generally can adopt the oxidizability component that feeds in the inert atmosphere eliminating system to realize.Described inert atmosphere is the conventional inert atmosphere that uses in this area, preferably is nitrogen and/or inert gas, more preferably is nitrogen.
In the step (1), the method for described oxidation and condition can be method and the condition of this area routine.The temperature of described oxidation preferably is 50～100 ℃, more preferably is 60～80 ℃.When described oxidation finished, the pH value of described solution preferably was 6.5～8.5, more preferably is 7.0～8.0.Described oxidation is preferably adopted in described solution and to be added oxidant and carry out.Described oxidant preferably is one or more in oxygen, ozone, hydrogen peroxide and the peroxosulphuric hydrogen salt.Described oxidant can add jointly with non-oxide component, for example adds with the form of the mist that contains oxidant and/or with the form of the solution that contains oxidant.Described peroxosulphuric hydrogen salt preferably is peroxosulphuric hydrogen sodium.The feeding speed of described oxidant preferably is: in gaseous oxidizer 1～10L/min or in on-gaseous oxidant 0.005～0.08mol/min.Described on-gaseous oxidant refers to liquid oxidizer and/or solid oxide agent.Among the present invention, the chemical formula of described complex chemical compound seed crystal preferably is Mn
3O
4Ni (OH)
2
In the step (2), described nickel salt can be the conventional nickel salt that uses in this area, preferably is in nickelous sulfate, nickel nitrate, nickel chloride and the nickel acetate one or more.Described manganese salt can be the conventional nickel salt that uses in this area, preferably is in manganese sulfate, manganese nitrate, manganese chloride and the manganese acetate one or more.Described alkali compounds is the conventional alkali compounds that uses in this area, preferably is in KOH, NaOH, LiOH and the ammoniacal liquor one or more, more preferably is NaOH.
In the step (2), by this area general knowledge, the process that described complex chemical compound seed crystal is grown up can be carried out continuously, also can carry out by substep.Therefore, the solution that contains described nickel salt and manganese salt can directly mix with described complex chemical compound seed crystal, also the solution that contains described nickel salt and manganese salt can be mixed with described complex chemical compound seed crystal in batches one by one.Correspondingly, the reaction of described nickel salt, manganese salt and alkali compounds also can be undertaken by the mode of full dose metathesis reaction or part metathesis reaction.The full dose metathesis reaction industrial be more favourable because finally do not have remaining unreacted nickel salt and manganese salt.In the part metathesis reaction, almost can not form the little complex chemical compound of particle diameter, so this method is favourable for the product that acquisition has uniform shapes and particle diameter distribution.Among the present invention, the reaction condition of the hybrid reaction of described nickel salt, manganese salt and alkali compounds preferably is: make the pH value of the reaction system of described nickel salt, manganese salt and described alkali compounds maintain 6.5～8.5, get final product.
In the step (2), the method for described oxidation and condition can be method and the condition of this area routine.The temperature of described oxidation preferably is 50～100 ℃, more preferably is 60～80 ℃.When described oxidation finished, the pH value of described solution preferably was 6.5～8.5, more preferably is 7.0～8.0.Described oxidation is preferably adopted in described solution and to be added oxidant and carry out.Described oxidant preferably is one or more in oxygen, ozone, hydrogen peroxide and the peroxosulphuric hydrogen salt.Described oxidant can add jointly with non-oxide component, for example adds with the form of the mist that contains oxidant and/or with the form of the solution that contains oxidant.Described peroxosulphuric hydrogen salt preferably is peroxosulphuric hydrogen sodium.The feeding speed of described oxidant preferably is: in gaseous oxidizer 1～10L/min or in on-gaseous oxidant 0.005～0.08mol/min.Described on-gaseous oxidant refers to liquid oxidizer and/or solid oxide agent.
In the step (2), by suitable setting reaction condition, as amount and the adding method of the alkali compounds that adds, can control the growth of seed crystal, uniform grading distributes and the crystal grain of uniform shapes thereby obtain to have.Among the present invention, the chemical formula of described crystal grain preferably is Mn
3O
4Ni (OH)
2
In the step (3), described lithiumation thing preferably is one or more in lithium hydroxide, lithium nitrate, lithium carbonate, lithium bicarbonate, lithium chloride and the lithium sulfate, more preferably is in lithium hydroxide, lithium carbonate and the lithium bicarbonate one or more.When the specific nickel manganate cathode material for lithium of preparation, wherein the reacting dose of the above-claimed cpd that the ratio of components of manganese, nickel and lithium can be by is correspondingly controlled.For example, when the crystal grain that replaces when proton and lithium compound reacted in liquid phase medium, the alkali concn of the reaction liquid that the reacting dose of two kinds of compounds can be by measuring a small amount of sampling was measured.
In the step (3), the described method of oxidation reaction and method and the condition that condition is this area routine of in oxidative environment, carrying out.Described oxidative environment is the environment that contains oxidizing gas, and described oxidizing gas preferably is one or more in air, oxygen and the ozone.The feeding speed of described oxidizing gas preferably is 0.5～5L/min.The time of described oxidation reaction preferably is 2～24h, more preferably is 5～16h.The temperature of described oxidation reaction preferably is 70～250 ℃, more preferably is 80～220 ℃, is 90～180 ℃ best.By this area general knowledge, when the temperature of described oxidation reaction was lower than 100 ℃, this oxidation reaction can under atmospheric pressure be carried out; When the temperature of described oxidation reaction surpassed 100 ℃, this oxidation reaction can be carried out in autoclave.
In the step (3), after described oxidation reaction, the step of preferably also washing.The method of described washing and condition can be method and the condition of this area routine.Described washing preferably adopts lithium hydroxide solution to carry out.The concentration of described lithium hydroxide solution preferably is 0.05～1mol/L.
In the step (3), described operation with acid treatment described crystal grain can make that the sub-fraction metal ion is replaced by hydrogen ion in the described crystal grain, and the hydrogen ion of replacement is active, can improve the follow-up reactivity with the lithiumation thing of crystal grain.The acid-treated acid of described usefulness can be inorganic acid and/or organic acid, preferably be in hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, acetic acid and the formic acid one or more, more preferably being in hydrochloric acid, nitric acid, sulfuric acid and the hydrofluoric acid one or more, is sulfuric acid and/or hydrochloric acid best.The concentration of the acid-treated acid of described usefulness preferably is 0.05～10mol/L.The described acid-treated time preferably is 0.5～5 hour.By this area general knowledge, after described acid treatment, filter to remove acid.The crystal grain that described proton replaces can carry out in liquid phase with mixing of lithium compound, perhaps also can solid phase mixing.The crystal grain that described proton replaces and the mixing of lithiumation thing are preferably carried out in liquid phase.
In the step (3), the method for described drying and condition can be method and the condition of this area routine.
In the step (4), the method for described roasting and condition can be method and the condition of this area routine.The temperature of described roasting preferably is more than 500 ℃, more preferably is 650～1000 ℃, is 750～950 ℃ best.The atmosphere of described roasting preferably is oxygen-containing atmosphere, more preferably is air or oxygen.The time of described roasting preferably is 6～24 hours.
By this area general knowledge, in the step (4), after described roasting, can also grind, operations such as fragmentation and compacting one or more.Those method of operating are not particularly limited, and for example can suppress by screen cloth make-up machine, single lead screw ex truding briquetting machine, edge runner, pressure roll, mixer-mill etc., and the stirring-granulating that perhaps uses mixer etc. to carry out carries out compacting.
Adopt preparation method of the present invention, prepared micron order monocrystalline nickel manganate cathode material for lithium belongs to the spinels positive electrode, and it has, and uniform particle diameter distributes and uniform grain shape.The single crystal grain average-size of described micron order monocrystalline nickel manganate cathode material for lithium is between 1～30 micron, and specific area is low, has higher packed density.
On the basis that meets this area general knowledge, above-mentioned each optimum condition, but combination in any namely get the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available getting all.
Positive progressive effect of the present invention is:
The preparation method of micron order monocrystalline nickel manganate cathode material for lithium of the present invention can control diameter and the shape of single crystal grain, the positive electrode that obtains has the micron order mono-crystalline structures, have bigger, uniform particle diameter, lattice defect is few and form even, make the positive electrode that makes not only have very high bulk density, also have high-energy-density, structural stability is good, have good cycle performance, its high-temperature behavior is compared with common nickel lithium manganate material and is greatly improved; The prepared positive electrode of this preparation method has three-dimensional channel regular and lithium ion transmission smoothly, reduced the obstruction of in the charge and discharge process lithium ion being moved, thereby have the ultra-high magnifications charge-discharge performance, be suitable in high power type lithium secondary batteries such as electric tool and hybrid electric vehicle, using.
Description of drawings
Fig. 1 is the X-ray diffractogram (XRD) of the micron order monocrystalline nickel manganate cathode material for lithium of embodiment 3.
Fig. 2 is the sem photograph (SEM) of the micron order monocrystalline nickel manganate cathode material for lithium of embodiment 3.
Fig. 3 is micron order monocrystalline nickel manganate cathode material for lithium and lithium metal and the 1M LiPF of embodiment 3
6The electrolyte of EC/DMC form the charging and discharging curve of CR2032 type button cell under different multiplying.
Fig. 4 is micron order monocrystalline nickel manganate cathode material for lithium preceding 500 all charging and discharging curves at normal temperatures of embodiment 3.
Fig. 5 is the preceding 250 all charging and discharging curves of micron order monocrystalline nickel manganate cathode material for lithium under 55 ℃ of embodiment 3.
Fig. 6 is the laser particle size distribution curve of the micron order monocrystalline nickel manganate cathode material for lithium of embodiment 3.
Embodiment
Mode below by embodiment further specifies the present invention, but does not therefore limit the present invention among the described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example according to conventional method and condition, or is selected according to catalogue.
A kind of preparation method of micron order monocrystalline nickel manganate cathode material for lithium, it comprises the steps:
(1) in stainless steel or plastics reactor, the sodium hydroxide solution that adds 12 liters of 8mol/L, again with the speed of 5L/min to wherein being blown into nitrogen, and to wherein adding 12 liters of aqueous solution that contain 3mol/L manganese sulfate and 1mol/L nickelous sulfate rapidly, stir 5h down in 70 ℃ and react, obtain nickel-manganese composite hydroxide; In the solution that contains nickel-manganese composite hydroxide, under stirring, feed the gaseous mixture of volume ratio 1:1 air and nitrogen with the speed of 5L/min, carry out oxidation in 70 ℃, reach 7.5 to the pH of solution, oxidation finishes, and obtains the complex chemical compound seed crystal;
(2-1) under stirring, speed with 5L/min in the solution that contains the complex chemical compound seed crystal feeds the air of volume ratio 1:1 and the mist of nitrogen, simultaneously under 70 ℃, in 16 hours, add 12L in the solution and contain the aqueous solution of 3mol/L manganese sulfate and 1mol/L nickelous sulfate and the sodium hydroxide solution of 11.99 liters of 8mol/L, to carry out metathesis reaction and oxidation reaction, make complex chemical compound seeded growth, keep the pH value of reaction system in the course of reaction 6.5～8.5, react to final pH and reach 7.5;
(2-2) extract 5 liters of slurries out, speed with 5L/min feeds the air of volume ratio 1:1 and the gaseous mixture of nitrogen in this slurry subsequently, in 16 hours, add simultaneously 12 liters and contain the aqueous solution of 3mol/L manganese sulfate and 1mol/L nickelous sulfate and the sodium hydroxide solution of 12.05 liters of 8mol/L reacts, keep the pH value of reaction system in the course of reaction 6.5～8.5, react to final pH and reach 7.5, the complex chemical compound seed crystal grow up to particle diameter be 0.1～10 micron; Filter and wash with water the solid in the collection slurry, get crystal grain;
(3) under stirring, crystal grain (counting 700g by Mn) is dispersed in the water, in 1 hour, add the sulfuric acid of 1.2 liters of 1mol/L, under 60 ℃, carry out acid treatment 2 hours, get the crystal grain that proton replaces; The crystal grain (counting 500g by Mn) that proton is replaced mixes with the hydronium(ion) oxidation lithium of 3.12mol, and to add water to liquor capacity be 1.2L, speed bubbling air with 2L/min, under stirring, reacted 5 hours down in 90 ℃, reactant mixture is transferred in the autoclave again and under 130 ℃, carried out hydrothermal treatment consists 5 hours, after hydrothermal treatment consists finishes, with the speed bubbling air of 2L/min, under stirring, reacted 1 hour down in 90 ℃ again, reaction is cooled to 60 ℃ after finishing, with the lithium hydroxide solution washing of 2 liters of 0.1mol/L, drying is 12 hours under 120 ℃, gets the nickel manganate precursor for lithium after filtering;
(4) with the roasting 12 hours in air under 900 ℃ of nickel manganate precursor for lithium, namely get micron order monocrystalline nickel manganate cathode material for lithium, its chemical formula is LiMn
1.5Ni
0.5O
4
This micron order monocrystalline nickel manganate cathode material for lithium also can further grind and compacting, for example grinds and compacting at small-sized edge runner.
Embodiment 2
A kind of preparation method of micron order monocrystalline nickel manganate cathode material for lithium, it comprises the steps:
(1) with embodiment 1;
(2-1) under stirring, speed with 5L/min in the solution that contains the complex chemical compound seed crystal feeds the air of volume ratio 1:1 and the mist of nitrogen, simultaneously under 70 ℃, in 16 hours, add 12L in the solution and contain the aqueous solution of 3mol/L manganese sulfate and 1mol/L nickelous sulfate and the sodium hydroxide solution of 11.99 liters of 8mol/L, to carry out metathesis reaction and oxidation reaction, make complex chemical compound seeded growth, keep the pH value of reaction system in the course of reaction 6.5～8.5, react to final pH and reach 7.5;
(2-2) extract 5 liters of slurries out, the operation in the repeating step in slurry (2-1) is reacted, and reacts to pH and reaches 7.5;
(2-3) extract 5 liters slurry again out, feed the air of volume ratio 1:1 and the gaseous mixture of nitrogen by the speed of the 5 liters/min speed with 5L/min in this slurry, simultaneously in 8 hours, contain the aqueous solution of 3mol/L manganese sulfate and 1mol/L nickelous sulfate and the sodium hydroxide solution of 12.05 liters of 8mol/L reacts to wherein adding 12 liters, keep the pH value of reaction system in the course of reaction 6.5～8.5, react to final pH and reach at 7.5 o'clock, the complex chemical compound seed crystal grow up to particle diameter be 0.1～20 micron; Filter and wash with water the solid in the collection slurry, get crystal grain;
Subsequent step is with embodiment 1.
A kind of preparation method of micron order monocrystalline nickel manganate cathode material for lithium, it comprises the steps:
(1) in stainless steel or plastics reactor, add 12 liters of aqueous solution that contain 3mol/L manganese sulfate and 1mol/L nickelous sulfate, again with the speed of 5L/min to wherein being blown into nitrogen, solution is heated to 70 ℃, in the sodium hydroxide solution that in 1 hour, adds 12 liters of 8mol/L under the stirring, stir 2h down in 70 ℃ and react, obtain nickel-manganese composite hydroxide; In the solution that contains nickel-manganese composite hydroxide, under stirring, feed the air of volume ratio 1:1 and the gaseous mixture of nitrogen with the speed of 5L/min, carry out oxidation in 70 ℃, reach 7.5 to the pH of solution, oxidation finishes, and obtains the complex chemical compound seed crystal;
(2-1) under stirring, speed with 5L/min in the solution that contains the complex chemical compound seed crystal feeds the air of volume ratio 1:1 and the mist of nitrogen, contain the aqueous solution of 3mol/L manganese sulfate and 1mol/L nickelous sulfate and the sodium hydroxide solution of 11.99 liters of 8mol/L in 16 hours, adding 12L under 70 ℃ simultaneously, to carry out metathesis reaction and oxidation reaction, make complex chemical compound seeded growth, keep the pH value of reaction system in the course of reaction 6.5～8.5, react to final pH and reach 7.5;
(2-2) extract 5 liters of slurries out, the operation in the repeating step in slurry (2-1) is reacted, and reacts to pH and reaches 7.5;
(2-3) extract 5 liters slurry again out, speed with 5L/min in this slurry feeds the air of volume ratio 1:1 and the gaseous mixture of nitrogen, in 16 hours, add simultaneously 12 liters and contain the aqueous solution of 3mol/L manganese sulfate and 1mol/L nickelous sulfate and the sodium hydroxide solution of 12.05 liters of 8mol/L reacts, keep the pH value of reaction system in the course of reaction 6.5～8.5, react to final pH and reach 7.5, the complex chemical compound seed crystal grow up to particle diameter be 0.1～30 micron; Filter and wash with water the solid in the collection slurry, get crystal grain;
Subsequent step is with embodiment 1.
The X-ray diffractogram of this micron order monocrystalline nickel manganate cathode material for lithium as shown in Figure 1, its sem photograph is seen Fig. 2.This micron order monocrystalline nickel manganate cathode material for lithium and lithium metal and 1M LiPF
6The electrolyte of EC/DMC form the charging and discharging curve of CR2032 type button cell under different multiplying and see Fig. 3, its preceding 500 all charging and discharging curves are at normal temperatures seen Fig. 4, its preceding 250 all charging and discharging curves under 55 ℃ are seen Fig. 5.The laser particle size distribution curve of this micron order monocrystalline nickel manganate cathode material for lithium is seen Fig. 6.
Embodiment 4
A kind of preparation method of micron order monocrystalline nickel manganate cathode material for lithium, it comprises the steps:
(1) with embodiment 3;
(2) under stirring, in the solution that contains the complex chemical compound seed crystal, speed with 5L/min feeds nitrogen, add 12L simultaneously and contain the aqueous solution of 3mol/L manganese sulfate and 1mol/L nickelous sulfate, and this solution is heated to 70 ℃, then under stirring condition, nitrogen is become the gaseous mixture of volume ratio 1:1 air and nitrogen, and the speed that keeps 5L/min feeds in the solution, the sodium hydroxide solution that in 24 hours, adds 12.05 liters of 8mol/L then in the solution, to carry out metathesis reaction and oxidation reaction, keep the pH value of reaction system in the course of reaction 6.5～8.5, react to final pH and reach 8.0, the complex chemical compound seed crystal grow up to particle diameter be 0.1～20 micron; Filter and wash with water the solid in the collection slurry, get crystal grain;
(3) under stirring, crystal grain (counting 700g by Mn) is dispersed in the water, in 1 hour, add the sulfuric acid of 1.2 liters of 1mol/L, under 60 ℃, carry out acid treatment 2 hours, get the crystal grain that proton replaces; The crystal grain (counting 500g by Mn) that proton is replaced mixes with the hydronium(ion) oxidation lithium of 3.12mol, and to add water to liquor capacity be 1.2L, speed bubbling air with 2L/min, under stirring, reacted 16 hours down in 90 ℃, reaction is cooled to 60 ℃ after finishing, and wash with the lithium hydroxide solution of 2 liters of 0.1mol/L the filtration back, drying is 12 hours under 120 ℃, gets the nickel manganate precursor for lithium;
Subsequent step is with embodiment 1.
A kind of preparation method of micron order monocrystalline nickel manganate cathode material for lithium, it comprises the steps:
(1) in stainless steel or plastics reactor, add 12 liters of aqueous solution that contain 2.9mol/L manganese sulfate and 1mol/L nickelous sulfate, again with the speed of 5L/min to wherein being blown into nitrogen, solution is heated to 60 ℃, the sodium hydroxide solution that under stirring, in 1 hour, adds 12 liters of 7.8mol/L in the solution, stir 2h down in 60 ℃ and react, obtain nickel-manganese composite hydroxide; In the solution that contains nickel-manganese composite hydroxide, under stirring, feed the air of volume ratio 1:1 and the gaseous mixture of nitrogen with the speed of 1L/min, carry out oxidation in 60 ℃, reach 7.0 to the pH of solution, oxidation finishes, and obtains the complex chemical compound seed crystal;
(2-1) under stirring, speed with 1L/min in the solution that contains the complex chemical compound seed crystal feeds the air of volume ratio 1:1 and the mist of nitrogen, simultaneously under 70 ℃, in 16 hours, add 12L in the solution and contain the aqueous solution of 2.9mol/L manganese sulfate and 1mol/L nickelous sulfate and the sodium hydroxide solution of 11.99 liters of 7.8mol/L, to carry out metathesis reaction and oxidation reaction, make complex chemical compound seeded growth, keep the pH value of reaction system in the course of reaction 6.5～8.5, react to final pH and reach 7.0;
(2-2) extract 5 liters of slurries out, speed with 1L/min in the slurry feeds the air of volume ratio 1:1 and the gaseous mixture of nitrogen, in 16 hours, add simultaneously 12 liters and contain the aqueous solution of 2.9mol/L manganese sulfate and 1mol/L nickelous sulfate and the sodium hydroxide solution of 12.05 liters of 7.8mol/L reacts, keep the pH value of reaction system in the course of reaction 6.5～8.5, react to final pH and reach 7.0, the complex chemical compound seed crystal grow up to particle diameter be 0.1～15 micron; Filter and wash with water the solid in the collection slurry, get crystal grain;
(3) under stirring, crystal grain (counting 500g by Mn) is mixed with the hydronium(ion) oxidation lithium of 3.12mol, adding water to liquor capacity is 1.0L, speed bubbling air with 0.5L/min, under stirring, reacted 5 hours down in 90 ℃, reactant mixture is transferred in the autoclave again and under 130 ℃, carried out hydrothermal treatment consists 20 hours, after hydrothermal treatment consists finishes, again with the speed bubbling air of 0.5L/min, under stirring, reaction is 1 hour under 60 ℃, and reaction finishes the back filtration, with the lithium hydroxide solution washing of 2 liters of 0.05mol/L, drying is 12 hours under 120 ℃, gets the nickel manganate precursor for lithium;
(4) with the roasting 6 hours in air under 950 ℃ of nickel manganate precursor for lithium, namely get micron order monocrystalline nickel manganate cathode material for lithium.
A kind of preparation method of micron order monocrystalline nickel manganate cathode material for lithium, it comprises the steps:
(1) in stainless steel or plastics reactor, add 12 liters of aqueous solution that contain 3.2mol/L manganese sulfate and 1mol/L nickelous sulfate, again with the speed of 5L/min to wherein being blown into nitrogen, under 80 ℃, stir, the sodium hydroxide solution that in 1 hour, adds 12.05 liters of 8.37mol/L in the solution, stir 2h down in 80 ℃ and react, obtain nickel-manganese composite hydroxide; In the solution that contains nickel-manganese composite hydroxide, under stirring, feed the air of volume ratio 1:1 and the gaseous mixture of nitrogen with the speed of 10L/min, carry out oxidation in 80 ℃, reach 8.0 to the pH of solution, oxidation finishes, and obtains the complex chemical compound seed crystal;
(2-1) under stirring, speed with 10L/min in the solution that contains the complex chemical compound seed crystal feeds the air of volume ratio 1:1 and the mist of nitrogen, simultaneously under 80 ℃, in 5 hours, add 12L in the solution and contain the aqueous solution of 3.2mol/L manganese sulfate and 1mol/L nickelous sulfate and the sodium hydroxide solution of 11.99 liters of 8.37mol/L, to carry out metathesis reaction and oxidation reaction, make complex chemical compound seeded growth, keep the pH value of reaction system in the course of reaction 6.5～8.5, react to final pH and reach 8.0;
(2-2) extract 5 liters of slurries out, feed the gaseous mixture of volume ratio 1:1 air and nitrogen in the slurry with the speed of 10L/min, in 5 hours, add simultaneously 12 liters and contain the aqueous solution of 3.2mol/L manganese sulfate and 1mol/L nickelous sulfate and the sodium hydroxide solution of 12.05 liters of 8.37mol/L reacts, keep the pH value of reaction system in the course of reaction 6.5～8.5, react to final pH and reach 8.0, the complex chemical compound seed crystal grow up to particle diameter be 0.1～10 micron; Filter and wash with water the solid in the collection slurry, get crystal grain;
(3) under stirring, crystal grain (counting 700g by Mn) is dispersed in the water, in 1 hour, add the sulfuric acid of 1.2 liters of 10mol/L, under 80 ℃, carry out acid treatment half an hour, get the crystal grain that proton replaces; The crystal grain (counting 500g by Mn) that will contain the proton replacement mixes with the hydronium(ion) oxidation lithium of 3.12mol, and to add water to liquor capacity be 1.2L, speed bubbling air with 5L/min, under stirring, reacted 5 hours down in 90 ℃, reactant mixture is transferred in the autoclave again and under 180 ℃, carried out hydrothermal treatment consists 1 hour, after hydrothermal treatment consists finishes, with the speed bubbling air of 5L/min, under stirring, reacted 1 hour down in 60 ℃ again, reaction finishes the back and filters, with the lithium hydroxide solution washing of 2 liters of 1mol/L, drying is 12 hours under 120 ℃, gets the nickel manganate precursor for lithium;
(4) with the roasting 24 hours in air under 700 ℃ of nickel manganate precursor for lithium, namely get micron order monocrystalline nickel manganate cathode material for lithium.
The comparative example 1
A kind of preparation method of nickel manganate cathode material for lithium, it comprises the steps:
(1) in stainless steel or plastics reactor, add 12 liters of aqueous solution that contain 3mol/L manganese sulfate and 1mol/L nickelous sulfate, again with the speed of 5L/min to wherein being blown into nitrogen, solution is heated to 70 ℃ and stirring, in 1 hour to the sodium hydroxide solution that wherein adds 12 liters of 8mol/L, stir 2h down in 70 ℃ and react, obtain nickel-manganese composite hydroxide; In the solution that contains nickel-manganese composite hydroxide, under stirring, feed the air of volume ratio 1:1 and the gaseous mixture of nitrogen with the speed of 5L/min, 70 ℃ are carried out oxidation, reach 7.0 to the pH of solution, and oxidation finishes, and obtains complex chemical compound;
(2) under stirring, above-mentioned complex chemical compound (counting 70g by Mn) is dispersed in the water, in 1 hour, add the sulfuric acid of 120 milliliters of 1mol/L, under 60 ℃, carry out acid treatment 2 hours, get the complex chemical compound crystal that proton replaces; The complex chemical compound crystal (counting 50g by Mn) that will contain the proton replacement mixes with the hydronium(ion) oxidation lithium of 0.312mol, and to add water to liquor capacity be 1.0L, speed bubbling air with 5L/min, under stirring, reacted 16 hours down in 90 ℃, reaction is cooled to 60 ℃ after finishing, and wash with the lithium hydroxide solution of 500 milliliters of 0.1mol/L the filtration back, drying is 12 hours under 120 ℃, gets the nickel manganate precursor for lithium;
(3) obtain the nickel LiMn2O4 according to the method identical with embodiment 1, but the nickel manganate precursor for lithium was 750 ℃ of roastings 24 hours.
The comparative example 2
A kind of preparation method of nickel manganate cathode material for lithium, it comprises the steps:
Obtain the nickel LiMn2O4 according to the method identical with comparative example 1, but the nickel manganate precursor for lithium was 950 ℃ of roastings 6 hours.
The comparative example 3
A kind of preparation method of nickel manganate cathode material for lithium, it comprises the steps:
(1) with comparative example 1;
(2) under stirring, above-mentioned complex chemical compound (counting 70g by Mn) is dispersed in the water, in 1 hour, add the sulfuric acid of 120 milliliters of 1mol/L, under 60 ℃, carry out acid treatment 2 hours, get the compoundizationization thing crystal that proton replaces; The complex chemical compound (counting 50g by Mn) that will contain the proton replacement mixes with the hydronium(ion) oxidation lithium of 0.281mol, and to add water to liquor capacity be 1.0L, speed bubbling air with 5L/min, under stirring, reacted 16 hours down in 90 ℃, reaction is cooled to 60 ℃ after finishing, and the filtration back got the nickel manganate precursor for lithium with the lithium hydroxide solution washing of 500 milliliters of 0.1mol/L down in dry 12 hours in 120 ℃;
(3) with the step among the embodiment 1 (4).
The comparative example 4
A kind of preparation method of nickel manganate cathode material for lithium, it comprises the steps:
(1) with comparative example 1;
(2) under stirring, above-mentioned complex chemical compound (counting 70g by Mn) is dispersed in the water, in 1 hour, add the sulfuric acid of 120 milliliters of 1mol/L, under 60 ℃, carry out acid treatment 2 hours, get the crystalline composite oxide that proton replaces; The complex chemical compound (counting 50g by Mn) that will contain the proton replacement mixes with the hydronium(ion) oxidation lithium of 0.388mol, and to add water to liquor capacity be 1.0, speed bubbling air with 5L/min, under stirring, reacted 16 hours down in 90 ℃, reaction is cooled to 60 ℃ after finishing, and filters the back with the lithium hydroxide solution washing of 500 milliliters of 0.1mol/L, gets the nickel manganate precursor for lithium;
(3) with the step among the embodiment 1 (4).
Effect embodiment
In order to measure the chemical property of nickel manganate cathode material for lithium, with above-mentioned synthetic nickel manganate cathode material for lithium and acetylene black and PVDF(polyvinylidene fluoride) be mixed and made into slurry at normal temperatures and pressures in the ratio of 87:8:5, evenly be coated on the aluminum substrates.The electrode slice that obtains at 120 ℃ down after the oven dry, is compressed under certain pressure, continue 120 ℃ of oven dry 12 hours down, then film being cut into area is 1cm
2Thin rounded flakes as positive pole.Be negative pole with the pour lithium slice, with 1M LiPF
6EC+DMC solution (volume ratio is 1:1) be electrolyte, in being full of the glove box of argon gas, be assembled into CR2032 type button cell, test result sees Table 1.Wherein, the reversible specific capacity of nickel manganate cathode material for lithium is measured under the charge-discharge magnification of 0.5C and 5C respectively, and the room temperature capability retention also at room temperature circulates respectively after 500 times and measures after the circulation 250 times down at 55 ℃.
The performance of the nickel manganate cathode material for lithium among each embodiment of table 1 and the comparative example
Claims (10)
1. the preparation method of a micron order monocrystalline nickel manganate cathode material for lithium, it comprises the steps:
(1) make nickel-manganese composite hydroxide in solution, the mol ratio of Mn:Ni is 2.9:1～3.2:1 in the described nickel-manganese composite hydroxide, and the described nickel-manganese composite hydroxide of oxidation gets the complex chemical compound seed crystal;
(2) under the situation that described complex chemical compound seed crystal exists, in the mol ratio of Mn:Ni be the ratio of 2.9:1～3.2:1 in solution with nickel salt, manganese salt and alkali compounds hybrid reaction, and carry out oxidation simultaneously, make described complex chemical compound seed crystal grow up to particle diameter be 0.1～30 micron, get crystal grain;
(3) be that the ratio of 3:1.8～3:2.3 is mixed in solution with described crystal grain and lithiumation thing in the mol ratio of Mn:Li, carry out oxidation reaction in oxidative environment, it is dry to filter the back, gets the presoma of nickel LiMn2O4 compound;
Perhaps, with the described crystal grain of acid treatment, get the crystal grain that proton replaces, the crystal grain that described proton is replaced and lithiumation thing are the ratio mixing of 3:1.8～3:2.3 in the mol ratio of Mn:Li then, in oxidative environment, carry out oxidation reaction, it is dry to filter the back, gets the presoma of nickel LiMn2O4 compound;
(4) presoma with described nickel LiMn2O4 compound carries out roasting, namely.
2. preparation method as claimed in claim 1 is characterized in that, in the step (1), the preparation method of described nickel-manganese composite hydroxide adopts following manner to carry out: under anaerobic voltinism environment, in water, nickel salt and manganese salt are mixed, with the alkali compounds reaction, get final product again;
And/or in the step (1), the temperature of described oxidation is 50～100 ℃;
And/or in the step (1), when described oxidation finished, the pH value of described solution was 6.5～8.5;
And/or in the step (1), described oxidation employing adds oxidant and carries out in described solution.
3. preparation method as claimed in claim 2 is characterized in that, in the step (1), described nickel salt is one or more in nickelous sulfate, nickel nitrate, nickel chloride and the nickel acetate; Described manganese salt is one or more in manganese sulfate, manganese nitrate, manganese chloride and the manganese acetate; Described alkali compounds is one or more in KOH, NaOH, LiOH and the ammoniacal liquor;
And/or in the step (1), the temperature of described oxidation is 60～80 ℃,
And/or in the step (1), when described oxidation finished, the pH value of described solution was 7.0～8.0;
And/or in the step (1), described oxidant is one or more in oxygen, ozone, hydrogen peroxide and the peroxosulphuric hydrogen salt; The feeding speed of described oxidant is: in gaseous oxidizer 1～10L/min or in on-gaseous oxidant 0.005～0.08mol/min.
4. preparation method as claimed in claim 1 is characterized in that, in the step (2), described nickel salt is one or more in nickelous sulfate, nickel nitrate, nickel chloride and the nickel acetate; Described manganese salt is one or more in manganese sulfate, manganese nitrate, manganese chloride and the manganese acetate; Described alkali compounds is one or more in KOH, NaOH, LiOH and the ammoniacal liquor;
And/or in the step (2), the reaction condition of the hybrid reaction of described nickel salt, manganese salt and alkali compounds is: make the pH value of the reaction system of described nickel salt, manganese salt and described alkali compounds maintain 6.5～8.5, get final product;
And/or in the step (2), the temperature of described oxidation is 50～100 ℃;
And/or in the step (2), when described oxidation finished, the pH value of described solution was 6.5～8.5;
And/or in the step (2), described oxidation employing adds oxidant and carries out in described solution.
5. preparation method as claimed in claim 4 is characterized in that, in the step (2), the temperature of described oxidation is 60～80 ℃;
And/or in the step (2), when described oxidation finished, the pH value of described solution was 7.0～8.0;
And/or in the step (2), described oxidant is one or more in oxygen, ozone, hydrogen peroxide and the peroxosulphuric hydrogen salt; The feeding speed of described oxidant is: in gaseous oxidizer 1～10L/min or in on-gaseous oxidant 0.005～0.08mol/min.
6. preparation method as claimed in claim 1 is characterized in that, in the step (3), described lithiumation thing is one or more in lithium hydroxide, lithium nitrate, lithium carbonate, lithium bicarbonate, lithium chloride and the lithium sulfate;
And/or in the step (3), described oxidative environment is the environment that contains oxidizing gas, and described oxidizing gas is one or more in air, oxygen and the ozone;
And/or in the step (3), the time of described oxidation reaction is 2～24h; The temperature of described oxidation reaction is 70～250 ℃;
And/or, in the step (3), after described oxidation reaction, the step of also washing;
And/or in the step (3), the acid-treated acid of described usefulness is one or more in hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, acetic acid and the formic acid;
And/or in the step (3), the concentration of the acid-treated acid of described usefulness is 0.05～10mol/L; The described acid-treated time is 0.5～5 hour;
And/or in the step (3), crystal grain and being blended in the liquid phase of lithiumation thing that described proton replaces are carried out.
7. preparation method as claimed in claim 6 is characterized in that, in the step (3), described lithiumation thing is one or more in lithium hydroxide, lithium carbonate and the lithium bicarbonate;
And/or the feeding speed of described oxidizing gas is 0.5～5L/min;
And/or in the step (3), the time of described oxidation reaction is 5～16h; The temperature of described oxidation reaction is 80～220 ℃;
And/or in the step (3), described washing adopts lithium hydroxide solution to carry out;
And/or in the step (3), the acid-treated acid of described usefulness is one or more in hydrochloric acid, nitric acid, sulfuric acid and the hydrofluoric acid.
8. preparation method as claimed in claim 7 is characterized in that, in the step (3), the temperature of described oxidation reaction is 90～180 ℃; And/or the concentration of described lithium hydroxide solution is 0.05～1mol/L; And/or the acid-treated acid of described usefulness is sulfuric acid and/or hydrochloric acid.
9. preparation method as claimed in claim 1 is characterized in that, in the step (4), the temperature of described roasting is more than 500 ℃; The atmosphere of described roasting is oxygen-containing atmosphere; The time of described roasting is 6～24 hours.
10. preparation method as claimed in claim 9 is characterized in that, in the step (4), the temperature of described roasting is 650～1000 ℃; The atmosphere of described roasting is air or oxygen.
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