CN107634196A - Adulterate the preparation method of the nickel-cobalt-manganese ternary material of zinc - Google Patents
Adulterate the preparation method of the nickel-cobalt-manganese ternary material of zinc Download PDFInfo
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Abstract
The present invention relates to the preparation method of the nickel-cobalt-manganese ternary material of doping zinc, it is characterised in that the compound of described zinc is zinc oxide, zinc chloride, zinc nitrate, zinc acetate, zinc carbonate, zinc hydroxide, basic zinc carbonate or zinc acetate basic.By nickel, cobalt, manganese and the compound mixing for adulterating zinc, compound, ammonification water, ageing, cooling, the drying and other steps for passing through wet-milling plus lithium prepare dry predecessor.Dry predecessor is placed in oxygen atmosphere, the tertiary cathode material for mixing zinc is made using programmed temperature method.The cost of material of the present invention is relatively low, and raw material sources are extensive, and preparation technology is simple, easy to operate, time-consuming few, the uniformity of the electrode material of preparation is good, and composition is uniform, with outstanding discharge performance, the cycle performance particularly to discharge under conditions of high current is good, is laid a good foundation for industrialization.
Description
Technical field
The invention belongs to technical field prepared by battery electrode material, be related to it is a kind of can be used for lithium battery, lithium ion battery,
The preparation method of the nickel-cobalt-manganese ternary material of polymer battery and ultracapacitor doping zinc.
Technical background
With the increasingly depleted of fossil energy, energy problem has become the focus of concern.Finding energy storage new material turns into
One of focus of research.The lithium ion battery of new energy storage system should have big voltage height, capacity, memory-less effect and long lifespan
The advantages that, it can be widely applied to the digital products such as mobile phone, digital camera, notebook computer and electric car, hybrid electric vehicle
Deng power tool.
Lithium ion battery includes positive electrode, negative material, barrier film, electrolyte and collector etc..Wherein, positive electrode is very
Big degree determines the performance of battery.The positive electrode of successful commercialization has cobalt acid lithium, LiMn2O4 and LiFePO4 etc..No
Cross, above-mentioned material also has many shortcomings, and finding the higher positive electrode of cost performance turns into study hotspot.1997, Ohzuku
Deng [Ohzuku T.et al., Chem.Lett., 1997,68：642.] take the lead in have studied LiNi1/3Mn1/3Co1/3O2Type ternary material
The performance of material.Research shows, this material fusion LiCoO2、LiNiO2And LiMn2O4The characteristics of, have reversible capacity it is high, into
This low, low toxin.Nickel-cobalt-manganese ternary material is represented by：LiNixCoyMnzO2(wherein, x+y+z=1).According to chemistry
Nickel, cobalt, the difference of manganese element mol ratio in formula, can be divided into different type by ternary material.Such as, the mol ratio (x: y of nickel, cobalt, manganese
: z) ternary material for being 3: 3: 3, referred to as 333 types；The ternary material that nickel, cobalt, the mol ratio of manganese are 5: 2: 3 is referred to as 523 types；Nickel,
The ternary material that cobalt, the mol ratio of manganese are 8: 1: 1 is referred to as 811 types, also similar other types etc..333 types, 523 types, 622
Type and 811 type ternary materials are respectively provided with α-NaFeO2Type layer structure.In ternary material, nickel, cobalt, the chemical valence point of manganese element
It is not+divalent ,+trivalent and+4 valencys.Ni is main active element.From the point of view of theoretically, the relative amount of nickel is higher, ternary material
Discharge capacity is higher.
[Koymaya Y., et al., J.Power Sources, 2003,119 (2) such as Koymaya：644-648.] research
Think, Li1-xNi1/3Co1/3Mn1/3O2Charging process with LiNi1/3Co1/3Mn1/3O2Exemplified by be：With the abjection of Li ions, have not
Same electronics is to reacting.As 0 ＜ x ＜ 1/3, Ni occurs2+/Ni3+Transformation；As 1/3 ＜ x ＜ 2/3, Ni occurs3+/
Ni4+Transformation；As 2/3 ＜ x ＜ 1, Co occurs3+/Co4+Transformation.
As 0 ＜ x ＜ 1/3
As 1/3 ＜ x ＜ 2/3
As 2/3 ＜ x ＜ 1:
For ternary material, when charging voltage is less than 4.3V (with respect to Li/Li+), Ni2+For main active substances, Co3 +It can improve the cyclicity and high rate performance of material, and Mn4+Oxidation-reduction reaction is not involved in cyclic process.
Due to xLi2MnO3·(1-x)LiMO2The structure and chemistry of solid solution (M=Ni, Co, Mn) material and ternary material
Composition is sufficiently close to, and statement of many documents to the structure of both materials is incorrect.For xLi2MnO3·(1-x)LiMO2Gu
For solution (M=Ni, Co, Mn), charging voltage<During 4.4V, Li in solid solution2MnO3Without electro-chemical activity [Yang F.,
Zhang Q.et al., Electrochim.Acta, 2015,165：182-190.].At this voltage, electrification is participated in during charging
Learn the LiMO in the mainly solid solution of reaction2。Li+From LiMO2Middle abjection, while M is oxidized to MO2.Put in this case
When electric, with Li+It is embedded, MO2LiMO can not be fully converted to2, cause part irreversible reaction.Work as charging voltage>During 4.4V,
The Li of solid solution2MnO32 Li that can deviate from+With O2-With reference to (actual abjection Li2O), the MnO of electro-chemical activity is produced2Phase；
In discharge process, the part Li that deviate from originally+Embedding it can return to MnO2In.[Chen C.J., et al., J.Am.Chem.Soc.,
2016,138：8824-8833.].It is visible from the discussion above, although ternary material and solid-solution material be respectively provided with stratiform α-
NaFeO2Structure and chemical composition is very close.But, the charging and discharging curve and XRD diffraction patterns of ternary material and solid-solution material
There is obvious difference.From the point of view of the discharge voltage of discharge and recharge and the relation curve of discharge capacity, when charging voltage is higher than 4.4V,
The charge specific capacity and specific discharge capacity of solid solution can significantly increase, and the feature of oblique line is presented in its discharge curve, without obvious
Discharge voltage plateau；, will not and charge specific capacity and specific discharge capacity can be only increased slightly ternary material in this case
Significantly increase, and S type features are presented in its discharge curve, there is obvious discharge voltage plateau.
In recent years spray drying and other preparation methods also attract attention, however, coprecipitation be still prepare nickel, cobalt,
The main method of manganese ternary material.The industrial value of other methods is all little.Simply it is discussed below.
Coprecipitation is that precipitating reagent and complexing agent are added in the mixed solution of a variety of cations, control precipitation nucleation and
Growth course, obtain the co-precipitation of controllable pattern and particle diameter.The co-precipitation of preparation is made by the operation such as filtering, dry again
Presoma.This presoma is mixed with lithium salts, then positive electrode is made by high-temperature sintering process.The reappearance of the synthetic method
Good, the composition for preparing product is uniform.Can be by controlling mixing speed, pH value, Aging Temperature, precipitating reagent, the precipitation of precipitation process
The methods of ratio of agent rate of addition, ammoniacal liquor and metal ion, prepares the co-precipitation of controllable pattern and particle diameter, solves solid phase and closes
The problems such as into method batch mixing inequality and wide particle diameter distribution.Coprecipitation is divided into hydroxide and carbonate co-precipitation.It is specific next
Say, transition metal ions is formed into precursor with hydroxide and carbonate deposition agent respectively precipitates, then is mixed with lithium salts, finally
Ternary material is made in sintering.Hydroxide coprecipitation step is synthesis of ternary material precursor common method.This method typically will
For NaOH as precipitating reagent, ammoniacal liquor controls the pH value of course of reaction by precipitating reagent as complexing agent, by controlling reaction temperature and
Mixing speed realizes the purpose of control precursor particle diameter and pattern, the final pattern and chemical property for controlling ternary material.
In preparation process, due to the intermediate product Mn (OH) of generation2It is unstable, easy oxidation by air, the performance of material is influenceed, because
This, prepares precursor process and needs to be passed through nitrogen and protected.The advantages of hydroxide coprecipitation step, by controlling reaction condition
Obtain the uniform precursor of particle diameter distribution；Shortcoming is preparation technology complexity.Material concentration, rate of addition, stirring in preparation process
Speed, pH value and reaction temperature can all have an impact to the tap density and particle size uniformity of material.The greatest problem of this method
It is：The deposition condition difference that nickel, cobalt, the hydroxide of manganese generation are co-precipitated is larger, if the dosage deficiency of the alkali of precipitation process, that
, nickel and cobalt ions may precipitate not exclusively；If the dosage of the alkali of precipitation process is excessive, then, the manganese ion of precipitation may be sent out
Raw dissolution phenomena so that the sample room temperature chemical composition of preparation is difficult to unanimously, and performance is difficult to unanimously.
Liang etc. [Liang L, et al., Electrochim Acta, 2014,130：82-89.] with NiSO4·6H2O、
CoSO4·7H2O and MnSO4·H2O is raw material, using 0.6mol/L ammoniacal liquor as complexing agent, 800r/min mixing speed and
Mixed uniformly spherical precursor is made under conditions of pH 11.2.By precursor by washing, filtering, drying and calcination step
Tap density is made and reaches 2.59g/cm3622 section bar material.Under 1C multiplying power electric currents and 2.8~4.3V voltage ranges, prepared sample
Product are 172.1mAhg in the specific discharge capacity of the 1st circulation-1, the capability retention of 100 circulations is respectively 94.3%.Wen Lei etc.
[Wen Lei, etc., Peking University's journal, 2006,42 (1)：12-17.] with LiOHH2O、NaHCO3、CoSO4·7H2O、NiSO4·
6H2O and MnSO4·5H2O is raw material, is prepared for carbonate precursor precipitation, prepared by scrubbed, filtering, dry and double sintering
Obtain LiNi1/3Mn1/3Co1/3O2Sample.Research shows that, in 2.5~4.4V voltage ranges, the electric discharge first of the sample of preparation is held
Measure as 162mAhg-1, there is good cycle performance.
[Mao Yuqin etc., the Chinese patent such as Mao Yuqin：CN 103972499A, 2014-08-06] first by soluble nickel salt, cobalt
Salt, aluminium salt and lithium salts prepare spherical LiNi with coprecipitation1-a-bCoaAlbO2Material, it is blended into nano-TiO2Powder, spray into cladding
LiNi is made in device1-a-bCoaAlbO2/TiO250 circulation capability retentions be higher than 99%.
Forefathers' research shows that material concentration, precipitating reagent rate of addition, mixing speed, pH value and reaction temperature are to prepare height
The key of the uniform ternary material of tap density, particle diameter distribution.[Zhou Xindong etc., the Chinese patent such as Zhou Xindong：CN
102244239A, 2011-11-11] nickel, cobalt, aluminum salt solution and lithium source be prepared for ball-type nickel cobalt aluminium ternary with secondary precipitation
Material, the sample of preparation have the big (3.02g/cm of tap density3) the advantages that.Further study showed that except prepared by co-precipitation
Composition, particle diameter and the particle diameter distribution of particle have an impact outer, the radial distribution of sample particle composition to the performance of the sample of preparation
Also there is significant impact to the performance of sample.Hua etc. [Hua C, et al., J.Alloys and Compounds, 2014,614：
264-270.] with NiSO4·6H2O、CoSO4·7H2O、MnSO4·5H2O is raw material, after being dissolved in circulation stirring kettle, is added
For ammoniacal liquor as complexing agent, it is 11.5 to add sodium hydroxide solution regulation pH.24h is stirred under 55 DEG C and 750rpm of rotating speed,
Hydroxide precursor is made.By obtained presoma filtering, washing, dry after, then with lithium hydroxide mixed calcining, be made group
811 type ternary materials of linear gradient.Research shows, from the kernel of sample particle to surface, nickel content gradually decreases, and manganese contains
Amount gradually increase.Under big multiplying power electric current, the discharge capacity and cycle performance of 811 type ternary materials of composition gradient distribution are obvious
Better than the equally distributed respective material of composition.Under 2.8~4.3 voltage range and 1C multiplying power electric currents, composition linear gradient point
The discharge capacity of 1st circulation of 811 type ternary materials of cloth is 185.2mAhg-1, 100 circulation capability retentions be
93.2%.
Hou etc. [Hou P.et al., J.Power Sources, 2014,265：174~181.] step-by-step precipitation method is passed through
Carry out sample preparation：Nickel, cobalt, the reactant solution that manganese mol ratio is 8: 1: 1 is pumped into reactor to form 811 cores, then be pumped into
Nickel, cobalt, the reactant solution that manganese mol ratio is 3: 3: 3, form the first shell；Then, then be pumped into nickel, cobalt, manganese mol ratio be 4: 2
: 2 reactant solution, form the second shell；It is 811 types that core composition, which is finally made, and shell composition is respectively the double of 333 and 422 types
The ternary material of shell.Under 4C multiplying power electric currents, the capability retention that the sample 300 of preparation circulates is 90.9%.
Guo builds etc. that [Guo builds, Chinese patent：CN 104979553A, 2015-10-14] by soluble nickel salt, cobalt salt, aluminium
LiNi is made with coprecipitation in salt, lithium carbonate or lithium hydroxidecCo1-c-dAldO2(the ＞ c+d of 0.5,0.5 ＞ d ＞ of c ＞ 0,1) is coated
LiNiaCo1-a-bAlbO2The positive electrode of (a ＞ 0.7,0.05 >=b >=0,1 ＞ a+b).Research shows, by the micron of cladding
LiNiaCo1-a-bAlbO2The cyclical stability and heat endurance of (a ＞ 0.7,0.05 >=b >=0,1 ＞ a+b) are significantly improved,
Flatulence rate substantially reduces.Micron LiNi0.8Co0.15Al0.05O2Tap density be 2.51g/cm3.In 3.0~4.3V voltage ranges
Under 0.1C multiplying power electric currents, the discharge capacity first of sample is 194.5mAh/g, first charge-discharge efficiency 91.9%.
But, although by above-mentioned improvement, the ternary material prepared at present there is a problem in that, such as electronic conductivity
Low, big multiplying power stability is poor, high voltage cycle stability is poor, cation mixing, high temperature performance difference etc..In view of the above-mentioned problems,
Its performance is mainly improved by doping, Surface coating and post processing at present.However, current actual improvement and unobvious.
The content of the invention
Prepared by coprecipitation added precipitating reagent in the solution of mixed metal salt, is total to two or more cations in solution
With precipitating, precipitation mixture or pure solid solution presoma are generated.Sample prepared by coprecipitation has particle size distribution
Narrow, the advantages that tap density is high, electrochemical performance.But, prepared by coprecipitation needs power consumption, the water consumptions such as filtered, washing
Preparation process.Produce substantial amounts of industrial wastewater.In Co-precipitation, the precipitating reagent of addition is difficult in each of solution
Part forms uniform concentration, makes precipitation particle agglomeration or forms uneven composition.Further, since the precipitation of nickel, cobalt, manganese salt
Concentration product difference is larger, and different ions deposition condition difference is larger.Dissolving easily occurred for manganese ion existing in strong alkali solution
As the stoichiometric proportion of predecessor is difficult to control, and influences the chemical property of different batches sample.In order to improve the technique of preparation
Condition, reduces the deficiency of preparation method, and the present invention prepares nickel-cobalt-manganese ternary material using direct precipitation method.To realize above-mentioned mesh
, the technical solution adopted in the present invention comprises the steps of：
According to nickel, cobalt, manganese, lithium, zinc ion mol ratio x：y：z：k：M weigh respectively the compound of nickel, the compound of cobalt,
The compound of the compound of manganese, the compound of lithium and zinc ion；By the compound of nickel, the compound of cobalt, the compound of manganese and zinc
The compound of ion is mixed to get mixture 1；The deionized water of 1~10 times of volume of the cumulative volume of mixture 1 is added, mixing is equal
It is even, add the compound of the lithium weighed, under conditions of continuously stirring be added dropwise ammoniacal liquor to solution acidity fall pH10.0~
In the range of 12.5, it is well mixed by mixing apparatus；In times of 60~90 DEG C of temperature ranges under the inert atmosphere of no oxygen
One temperature is aged 5~48 hours, is cooled to room temperature, obtained mixture is predecessor 2；By predecessor 2 in less than 1 atmospheric pressure
Any temperature heating under the vacuum condition of power in 150~260 DEG C of sections is made the predecessor 3 of drying or using spray drying
Any temperature of the method in 150~260 DEG C of sections prepare dry predecessor 3；Dry predecessor 3 is placed in oxygen atmosphere
In, it is made using programmed temperature method and mixes zinc tertiary cathode material.
The compound of the nickel weighed, the compound of cobalt, the compound of manganese, the compound of the compound of lithium and zinc ion
In two or more compound be soluble in water.
Described nickel, cobalt, manganese, lithium, the mol ratio x of zinc ion：y：z：k：M meets following relation：
x：y：z：M=(0.45~0.51)：(0.18~0.20)：(0.28~0.30)：(0.001~0.06), 0.95≤k
≤ 1.10, and x+y+z+m=1；
Or x：y：z：M=(0.55~0.61)：(0.18~0.20)：(0.18~0.20)：(0.001~0.06), 0.95
≤ k≤1.10, and x+y+z+m=1；
Or x：y：z：M=(0.75~0.81)：(0.09~0.10)：(0.09~0.10)：(0.001~0.06), 0.95
≤ k≤1.10, and x+y+z+m=1.
Described ternary material meets following characteristics simultaneously：Diffraction maximum on XRD diffraction patterns with JCPDS cards 09-
0063 stratiform α-NaFeO2The characteristic diffraction peak of structure matches；Button half-cell prepared by material in 0.2C multiplying powers electric current and
Under 1st charge and discharge cycles, it is less than 15% with respect to ratio of the lithium electrode constant current charge to 4.6V than 4.4V increase charge specific capacities；
20~25 ° of the 2 θ angles section of sample XRD diffraction patterns does not correspond to JCPDS cards 27-1252 Li2MnO3Diffraction maximum.
Described programmed temperature method is carried out as follows：Dry predecessor 3 is placed in oxygen atmosphere, according to 0.1~10 DEG C/
Min speed is heated to any temperature of 790~880 DEG C of temperature ranges from room temperature program, is cooled to room temperature, is made and mixes zinc ternary
Positive electrode.
The compound of described nickel is nickel hydroxide, nickel nitrate, nickel chloride, basic nickel carbonate, nickel acetate or nickelous carbonate.
The compound of described cobalt is cobalt oxide, cobaltous fluoride, citric acid cobalt, cobalt nitrate, cobalt chloride, cobalt acetate or carbonic acid
Cobalt.
The compound of described manganese is manganous hydroxide, manganese carbonate, manganese citrate, manganese nitrate, manganese chloride or manganese acetate.
The compound of described lithium is lithium fluoride, lithium citrate, lithium nitrate, lithium chloride, lithium carbonate, lithium acetate or hydroxide
Lithium.
The compound of described zinc is zinc oxide, zinc chloride, zinc nitrate, zinc acetate, zinc carbonate, zinc hydroxide, alkali formula carbon
Sour zinc or zinc acetate basic.
Described spray drying process is the drying in any temperature progress of 150~260 DEG C of temperature ranges.
Described inert atmosphere is nitrogen, argon gas or helium.
Described mixing apparatus is ball milling or sand milling device.
The cost of material of the present invention is relatively low, and raw material sources are extensive, and preparation technology is simple, easy to operate, takes few.With it is coprecipitated
Shallow lake method is compared, and the sewage of preparation process discharge significantly reduces, and LiMn is not present in the sample of preparation6Superlattice structure, relatively
Lithium electrode constant current charge to 4.6V than 4.4V increase charge specific capacity ratio be less than 15%, the electrode material of preparation it is consistent
Property it is good, composition is uniform, has outstanding discharge performance, the cycle performance particularly to discharge under conditions of high current is good, is industry
Change is laid a good foundation.
With application this project team early stage be related to solid solution preparation patent of invention (ZL201210391584.0,
201210391629.4 201210391413.8,201210391672.0,201210391441.x) compare, patent of the present invention is
Form entirely different patent.From the point of view of structure, LiMn is not present in sample prepared by the application6Superlattice structure, and solid solution
LiMn be present in the structure of sample6Superlattice structure；From the point of view of the chemical composition of sample, 523,622,811 type ternary materials
Composition is respectively close to Li [Ni0.5Co0.2Mn0.3]O2、Li[Ni0.6Co0.2Mn0.2]O2、Li[Ni0.8Co0.1Mn0.1]O2；And solid solution
xLi2MnO3(1-x)Li[NiyMnzCok]O2Chemical formula be Li(1+x)[Ni(1-x)yCo(1-x)kMn(x+z-xz)]O(2+x).If it is considered that
Chemical formula xLi in patent ZL201210391584.02MnO3(1-x)Li[NiyMnzCok]O2Span, can be calculated
The theory of its solid solution sample, which forms, is：Li：Ni：Co：Mn：O mol ratios are (1~1.39)：(0.0173~0.333)：
(0.0174~0.443)：(0.204~0.952)：(1.87~2.26).The reason of the solid solution patent of this project team application early stage
There is similar situation with patent ZL201210391584.0 by composition, therefore, the application patent and the solid solution of application early stage
Although chemical formula has some similar places, but both are entirely different innovation and creation.
Brief description of the drawings
Fig. 1 is the XRD diffraction patterns of sample prepared by the embodiment of the present invention 1.
Fig. 2 be the embodiment of the present invention 1 prepare sample 2.5 to 4.3V voltage ranges, under 1C multiplying power electric currents the 1st circulation
Discharge curve.
Fig. 3 is that electric discharge of the sample of the preparation of the embodiment of the present invention 1 under 2.5 to 4.3V voltage ranges and 1C multiplying power electric currents is held
Amount and the graph of relation of cycle performance.
Embodiment
The present invention is further detailed with reference to embodiment.Embodiment is only the further supplement to the present invention
And explanation, rather than the limitation to invention.
Embodiment 1
According to nickel, cobalt, manganese, lithium, the mol ratio 0.5 for adulterating zinc ion：0.20：0.29：1：0.01 weighs hydroxide respectively
Nickel, cobalt acetate, manganese carbonate, lithium hydroxide and zinc oxide.Nickel hydroxide, cobalt acetate, manganese carbonate and zinc oxide are mixed to get mixed
Compound 1.The deionized water of 2 times of volumes of the cumulative volume of mixture 1 is added, is well mixed, the lithium hydroxide weighed is added, continuous
It is pH 12.0 that ammoniacal liquor to solution acidity is added dropwise under conditions of stirring, is well mixed by ball-grinding machine.In nitrogen atmosphere and 83 DEG C
Lower ageing 24 hours, is cooled to room temperature, obtained mixture is predecessor 2.By predecessor 2 0.1 atmospheric pressure vacuum
Under the conditions of in 230 DEG C of heating dry predecessor 3 is made.Predecessor 3 is placed in oxygen atmosphere, with 5 DEG C/min speed from
Room temperature is heated to 850 DEG C, is cooled to room temperature, and being made has stratiform α-NaFeO2Structure mixes zinc tertiary cathode material.Described
Ternary material meets following characteristics simultaneously：Diffraction maximum on XRD diffraction patterns with stratiform α-NaFeO2The characteristic diffraction peak of structure
(JCPDS card 09-0063) matches；Button half-cell prepared by ternary material is in 0.2C multiplying powers electric current and the 1st cycle charge discharge
Under electricity, with respect to lithium electrode constant current charge to 4.6V than 4.4V increase charge specific capacity ratio be 10%；The XRD diffraction of sample
There is not weak diffraction maximum in 20~25 ° of the 2 θ angles section of figure, not corresponding to Li2MnO3Diffraction maximum (JCPDS caused by diffraction
Card 27-1252).
Embodiment 2
According to nickel, cobalt, manganese, lithium, zinc ion mol ratio 0.45：0.20：0.30：0.95：0.05 weighs hydroxide respectively
Nickel, cobalt nitrate, manganous hydroxide, lithium citrate and zinc chloride.Nickel hydroxide, cobalt nitrate, manganous hydroxide and zinc chloride are mixed
To mixture 1.The deionized water of 1 times of volume of the cumulative volume of mixture 1 is added, is well mixed, adds the lithium citrate weighed,
Ammoniacal liquor is added dropwise under conditions of continuously stirring to solution acidity pH 12.5, is well mixed by sand milling device.In argon gas atmosphere and 60
It is aged 5 hours at DEG C, is cooled to room temperature, obtained mixture is predecessor 2.Predecessor 2 is used into spray drying process at 150 DEG C
Prepare dry predecessor 3.Predecessor 3 is placed in oxygen atmosphere, 880 are heated to from room temperature program with 10 DEG C/min speed
DEG C, room temperature is cooled to, being made has stratiform α-NaFeO2Structure mixes zinc tertiary cathode material.
Described ternary material meets following characteristics simultaneously：Diffraction maximum on XRD diffraction patterns with stratiform α-NaFeO2Knot
The characteristic diffraction peak (JCPDS card 09-0063) of structure matches；Button half-cell prepared by the ternary material of preparation is at 0.2C times
Under rate electric current and the 1st cycle charge-discharge, with respect to ratio of the lithium electrode constant current charge to 4.6V than 4.4V increase charge specific capacities
For 12%；There is not weak diffraction maximum in 20~25 ° of the 2 θ angles section of the XRD diffraction patterns of sample, not corresponding to Li2MnO3Spread out
Penetrate caused diffraction maximum (JCPDS card 27-1252).
Embodiment 3
According to nickel, cobalt, manganese, lithium, zinc ion mol ratio 0.48：0.18：0.28：1.10：0.06 weigh respectively nickel nitrate,
Cobalt carbonate, manganese nitrate, lithium nitrate and zinc nitrate.Nickel nitrate, cobalt carbonate, manganese nitrate and zinc nitrate are mixed to get mixture 1.Add
Enter the deionized water of 10 times of volumes of the cumulative volume of mixture 1, be well mixed, the lithium nitrate weighed added, in the bar continuously stirred
It is pH 10.0 that ammoniacal liquor to solution acidity is added dropwise under part, is well mixed by ball mill, and it is small that 48 are aged at helium atmosphere and 90 DEG C
When, room temperature is cooled to, obtained mixture is predecessor 2.By predecessor 2 under the vacuum condition of 0.9 atmospheric pressure in 260
Dry predecessor 3 is made in DEG C heating.Predecessor 3 is placed in oxygen atmosphere, is heated to 0.1 DEG C/min speed by room temperature
790 DEG C, room temperature is cooled to, being made has stratiform α-NaFeO2Structure mixes zinc tertiary cathode material.
Described ternary material meets following characteristics simultaneously：Diffraction maximum on XRD diffraction patterns with stratiform α-NaFeO2Knot
The characteristic diffraction peak (JCPDS card 09-0063) of structure matches；Button half-cell prepared by the ternary material of preparation is at 0.2C times
Under rate electric current and the 1st cycle charge-discharge, with respect to ratio of the lithium electrode constant current charge to 4.6V than 4.4V increase charge specific capacities
For 8%；There is not weak diffraction maximum in 20~25 ° of the 2 θ angles section of the XRD diffraction patterns of sample, not corresponding to Li2MnO3Diffraction
Caused diffraction maximum (JCPDS card 27-1252).
Embodiment 4
According to nickel, cobalt, manganese, lithium, zinc ion mol ratio 0.57：0.20：0.20：1.05：0.03 weigh respectively nickel chloride,
Cobalt chloride, manganese acetate, lithium nitrate and zinc chloride.Nickel chloride, cobalt chloride, manganese acetate and zinc chloride are mixed to get mixture 1.Add
Enter the deionized water of 10 times of volumes of the cumulative volume of mixture 1, be well mixed, the lithium nitrate weighed added, in the bar continuously stirred
It is pH 10 that ammoniacal liquor to the acidity of solution is added dropwise under part, is well mixed by sand milling device, 40 are aged at argon gas atmosphere and 60 DEG C
Hour, room temperature is cooled to, obtained mixture is predecessor 2.By predecessor 2 under the vacuum condition of 0.01 atmospheric pressure,
Dry predecessor 3 is made in 260 DEG C of heating.Predecessor 3 is placed in oxygen atmosphere, with 10 DEG C/min speed from room temperature journey
Sequence is heated to 790 DEG C, is cooled to room temperature, and being made has stratiform α-NaFeO2Structure mixes zinc tertiary cathode material.
Described ternary material meets following characteristics simultaneously：Diffraction maximum on XRD diffraction patterns with stratiform α-NaFeO2Knot
The characteristic diffraction peak (JCPDS card 09-0063) of structure matches；Button half-cell prepared by the ternary material of preparation is at 0.2C times
Under the discharge and recharge of rate electric current and the 1st circulation, with respect to ratio of the lithium electrode constant current charge to 4.6V than 4.4V increase charge specific capacities
Rate is 11%；There is not weak diffraction maximum in 20~25 ° of the 2 θ angles section of the XRD diffraction patterns of sample, not corresponding to Li2MnO3
Diffraction maximum caused by diffraction (JCPDS card 27-1252).
Embodiment 5
According to nickel, cobalt, manganese, lithium, zinc ion mol ratio 0.61：0.195：0.194：1.10：0.001 weighs hydrogen-oxygen respectively
Change nickel, cobalt oxide, manganese chloride, lithium carbonate and zinc acetate.Nickel hydroxide, cobalt oxide manganese chloride and zinc acetate are mixed to get mixing
Thing 1.The deionized water of 5 times of volumes of the cumulative volume of mixture 1 is added, is well mixed, is added the lithium carbonate weighed, continuously stirring
Under conditions of be added dropwise ammoniacal liquor to solution acidity be pH 10.0, be well mixed by sand milling device.It is old at nitrogen atmosphere and 80 DEG C
Change 48 hours, be cooled to room temperature, obtained mixture is predecessor 2.By predecessor 2 0.1 atmospheric pressure vacuum condition
Under in 150 DEG C of heating dry predecessor 3 is made.Predecessor 3 is placed in oxygen atmosphere, with 0.2 DEG C/min speed from room
Warm program is heated to 870 DEG C, is cooled to room temperature, and being made has stratiform α-NaFeO2Structure mixes zinc tertiary cathode material.
Described ternary material meets following characteristics simultaneously：Diffraction maximum on XRD diffraction patterns with stratiform α-NaFeO2Knot
The characteristic diffraction peak (JCPDS card 09-0063) of structure matches；Button half-cell prepared by the ternary material of preparation is at 0.2C times
Under rate electric current and the 1st cycle charge-discharge, with respect to ratio of the lithium electrode constant current charge to 4.6V than 4.4V increase charge specific capacities
For 10%；There is not weak diffraction maximum in 20~25 ° of the 2 θ angles section of the XRD diffraction patterns of sample, not corresponding to Li2MnO3Spread out
Penetrate caused diffraction maximum (JCPDS card 27-1252).
Embodiment 6
According to nickel, cobalt, manganese, lithium, zinc ion mol ratio 0.81：0.10：0.10：1.10：0.06 weigh respectively nickelous carbonate,
Cobalt carbonate, manganese nitrate, lithium acetate and zinc acetate.Nickelous carbonate, cobalt carbonate, manganese nitrate and zinc acetate are mixed to get mixture 1.Add
Enter 1 times of deionized water of the cumulative volume of mixture 1, be well mixed, add the lithium acetate weighed.Dripped under conditions of continuously stirring
Ammonification water to solution acidity is pH 12.5, is well mixed by ball milling mixing equipment.It is small in argon gas atmosphere and 90 DEG C of ageings 48
When, room temperature is cooled to, obtained mixture is predecessor 2.Predecessor 2 is prepared into drying at 260 DEG C with spray drying process
Predecessor 3.Predecessor 3 is placed in oxygen atmosphere, 880 DEG C is heated to from room temperature with 10 DEG C/min firing rate, is cooled to
Room temperature, being made has stratiform α-NaFeO2Structure mixes zinc tertiary cathode material.
Described ternary material meets following characteristics simultaneously：Diffraction maximum on XRD diffraction patterns with stratiform α-NaFeO2Knot
The characteristic diffraction peak (JCPDS card 09-0063) of structure matches；Button half-cell prepared by the ternary material of preparation is at 0.2C times
Under rate electric current and the 1st cycle charge-discharge, with respect to ratio of the lithium electrode constant current charge to 4.6V than 4.4V increase charge specific capacities
For 13%；There is not weak diffraction maximum in 20~25 ° of the 2 θ angles section of the XRD diffraction patterns of sample, not corresponding to Li2MnO3Spread out
Penetrate caused diffraction maximum (JCPDS card 27-1252).
Embodiment 7
According to nickel, cobalt, manganese, lithium, zinc ion mol ratio 0.78：0.09：0.09：1：0.04 weighs nickel acetate, chlorine respectively
Change cobalt, manganese carbonate, lithium nitrate and zinc carbonate.Nickel acetate, cobalt chloride, manganese carbonate and zinc carbonate are mixed to get mixture 1.Add
The deionized water of 5 times of volumes of the cumulative volume of mixture 1, it is well mixed, the lithium nitrate weighed is added, under conditions of continuously stirring
Ammoniacal liquor is added dropwise to solution acidity pH 12.0, is well mixed by general milling machine, is aged 24 hours in argon gas atmosphere and 60 DEG C,
Room temperature is cooled to, predecessor 2 is made.Predecessor 2 is prepared into dry predecessor 3 at 150 DEG C with spray drying process.By forerunner
Thing 3 is placed in oxygen atmosphere, is heated to 870 DEG C from room temperature with 0.5 DEG C/min firing rate, is cooled to room temperature, and being made has
Stratiform α-NaFeO2The tertiary cathode material for mixing zinc of structure.
Described ternary material meets following characteristics simultaneously：Diffraction maximum on XRD diffraction patterns with stratiform α-NaFeO2Knot
The characteristic diffraction peak (JCPDS card 09-0063) of structure matches；Button half-cell prepared by the ternary material of preparation is at 0.2C times
Under rate electric current and the 1st cycle charge-discharge, with respect to ratio of the lithium electrode constant current charge to 4.6V than 4.4V increase charge specific capacities
For 10%；There is not weak diffraction maximum in 20~25 ° of the 2 θ angles section of the XRD diffraction patterns of sample, not corresponding to Li2MnO3Spread out
Penetrate caused diffraction maximum (JCPDS card 27-1252).
Claims (9)
1. adulterate the preparation method of the nickel-cobalt-manganese ternary material of zinc, it is characterised in that：Rubbed according to nickel, cobalt, manganese, lithium, zinc ion
You compare x：y：z：k：M weighs the change of the compound of nickel, the compound of cobalt, the compound of manganese, the compound of lithium and zinc ion respectively
Compound；The compound of the compound of nickel, the compound of cobalt, the compound of manganese and zinc ion is mixed to get mixture 1；Add mixed
The deionized water of 1~10 times of volume of the cumulative volume of compound 1, it is well mixed, adds the compound of the lithium weighed, continuously stirring
Under conditions of be added dropwise ammoniacal liquor to solution acidity fall in the range of pH 10.0~12.5, be well mixed by mixing apparatus；Do not having
There is any temperature under the inert atmosphere of oxygen in 60~90 DEG C of temperature ranges to be aged 5~48 hours, be cooled to room temperature, it is obtained
Mixture is predecessor 2；By predecessor 2 under the vacuum condition less than 1 atmospheric pressure in any in 150~260 DEG C of sections
Temperature heating is made the predecessor 3 of drying or prepared using any temperature of the method being spray-dried in 150~260 DEG C of sections
Dry predecessor 3；Dry predecessor 3 is placed in oxygen atmosphere, is made using programmed temperature method and mixes zinc tertiary cathode material
Material；
Two in the described compound for weighing nickel compound, the compound of cobalt, the compound of manganese, the compound of lithium and zinc ion
Kind or two or more compounds are soluble in water；
Described nickel, cobalt, manganese, lithium, the mol ratio x of zinc ion：y：z：k：M meets following relation simultaneously：
x：y：z：M=(0.45~0.51)：(0.18~0.20)：(0.28~0.30)：(0.001~0.06), 0.95≤k
≤ 1.10, and x+y+z+m=1；
Or (0.55~0.61)：(0.18~0.20)：(0.18~0.20)：(0.001~0.06), 0.95≤k≤1.10, and x
+ y + z + m = 1；
Or (0.75~0.81)：(0.09~0.10)：(0.09~0.10)：(0.001~0.06), 0.95≤k≤1.10, and x
+ y + z + m = 1；
Described ternary material meets following characteristics simultaneously：Diffraction maximum on XRD diffraction patterns with JCPDS cards 09-0063
Stratiform α-NaFeO2The characteristic diffraction peak of structure matches；Button half-cell prepared by material is in 0.2C multiplying powers electric current and the 1st
Under charge and discharge cycles, it is less than 15% with respect to ratio of the lithium electrode constant current charge to 4.6V than 4.4V increase charge specific capacities；Sample
20~25 ° of the 2 θ angles section of XRD diffraction patterns does not correspond to JCPDS cards 27-1252 Li2MnO3Diffraction maximum.
2. the preparation method of the nickel-cobalt-manganese ternary material of doping zinc according to claim 1, it is characterised in that described journey
Sequence temperature-raising method is carried out as follows：Dry predecessor 3 is placed in oxygen atmosphere, according to 0.1~10 DEG C/min speed from room temperature
Program is heated to any temperature of 790~880 DEG C of temperature ranges, is cooled to room temperature, is made and mixes zinc tertiary cathode material.
3. the preparation method of the nickel-cobalt-manganese ternary material of doping zinc according to claim 1, it is characterised in that described nickel
Compound be nickel hydroxide, nickel nitrate, nickel chloride, basic nickel carbonate, nickel acetate or nickelous carbonate.
4. the preparation method of the nickel-cobalt-manganese ternary material of doping zinc according to claim 1, it is characterised in that described cobalt
Compound be cobalt oxide, cobaltous fluoride, citric acid cobalt, cobalt nitrate, cobalt chloride, cobalt acetate or cobalt carbonate.
5. the preparation method of the nickel-cobalt-manganese ternary material of doping zinc according to claim 1, it is characterised in that described manganese
Compound be manganous hydroxide, manganese carbonate, manganese citrate, manganese nitrate, manganese chloride or manganese acetate.
6. the preparation method of the nickel-cobalt-manganese ternary material of doping zinc according to claim 1, it is characterised in that described lithium
Compound be lithium fluoride, lithium citrate, lithium nitrate, lithium chloride, lithium carbonate, lithium acetate or lithium hydroxide.
7. the preparation method of the nickel-cobalt-manganese ternary material of doping zinc according to claim 1, it is characterised in that described zinc
Compound be zinc oxide, zinc chloride, zinc nitrate, zinc acetate, zinc carbonate, zinc hydroxide, basic zinc carbonate or zinc acetate basic.
8. the preparation method of the nickel-cobalt-manganese ternary material of doping zinc according to claim 1, it is characterised in that described is lazy
Property atmosphere is nitrogen, argon gas or helium.
9. the preparation method of the nickel-cobalt-manganese ternary material of doping zinc according to claim 1, it is characterised in that described is mixed
It is ball milling or sand milling device to close equipment.
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