CN107634204A - The method that high dispersive graphene improves rare earth doped nickel-cobalt-manganese ternary material property - Google Patents
The method that high dispersive graphene improves rare earth doped nickel-cobalt-manganese ternary material property Download PDFInfo
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Abstract
Improve the method for rare earth doped nickel-cobalt-manganese ternary material property the present invention relates to high dispersive graphene, it is characterised in that：Graphene powder is mixed with activating agent, by the rare earth doped ternary material for mixing, washing, filter, humidifying grinding media, be mixed into the obtained high dispersive graphene improvement of the steps such as doping ternary, drying, cooling, sintering.Described Doped ions are the ions of lanthanum, cerium, praseodymium, gadolinium, scandium or yttrium.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.Compared with coprecipitation method, the sewage of preparation process discharge significantly reduces, and LiMn is not present in the sample of preparation6Superlattice structure, the uniformity of the electrode material of preparation is good, and composition is uniform, has 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 method of the rare earth doped nickel-cobalt-manganese ternary material property of polymer battery and ultracapacitor.
Technical background
With the exhaustion of fossil energy, energy problem has become the focus of concern.Finding energy storage new material turns into research
One of focus.The lithium ion battery of new energy storage system should have that voltage is high, capacity is big, memory-less effect and long lifespan etc. are excellent
Point, it is dynamic to can be widely applied to the digital products such as mobile phone, digital camera, notebook computer and electric car, hybrid electric vehicle etc.
Power instrument.
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
The performance of ternary material.Research shows, this material fusion LiCoO2、LiNiO2And LiMn2O4The characteristics of, there is reversible appearance
Amount is high, cost is low, low toxin.Nickel-cobalt-manganese ternary material is represented by：LiNixCoyMnzO2(wherein, x+y+z
= 1).According to nickel in chemical formula, cobalt, manganese element mol ratio difference, ternary material can be divided into different type.Such as, nickel, cobalt,
The mol ratio of manganese（x∶y∶z）For 3: 3: 3 ternary material, referred to as 333 types；The ternary material that nickel, cobalt, the mol ratio of manganese are 5: 2: 3
Material is referred to as 523 types；The ternary material that nickel, 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 types and 811 type ternary materials are respectively provided with α-NaFeO2Type layer structure.In ternary material, nickel, cobalt,
The chemical valence of manganese element is+divalent ,+trivalent and+4 valencys respectively.Ni is main active element.From the point of view of theoretically, the relative of nickel contains
Amount is higher, and the discharge capacity of ternary material is higher.
Due to xLi2MnO3·(1-x)LiMO2Structure and the change of solid solution (M=Ni, Co, Mn) material and ternary material
Learn composition to be sufficiently close to, statement of many documents to the structure of both materials is incorrect.For xLi2MnO3·(1-x)LiMO2
For solid 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.].In the voltage
Under, the LiMO in the mainly solid solution of electrochemical reaction is participated in during charging2。Li+From LiMO2Middle abjection, while M is oxidized to
MO2.Discharge in this case, with Li+It is embedded, MO2LiMO can not be fully converted to2, cause part irreversible reaction.When
Charging voltage>During 4.4V, the Li of solid solution2MnO32 Li that can deviate from+With O2-With reference to（Actual abjection Li2O）, produce electrochemistry
The MnO of activity2Phase；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
Body material is respectively provided with stratiform α-NaFeO2Structure and chemical composition is very close.But, ternary material and solid-solution material fill
Discharge curve and XRD diffraction patterns have obvious difference.From the point of view of the discharge voltage of discharge and recharge and the relation curve of discharge capacity, when
When charging voltage is higher than 4.4V, the charge specific capacity and specific discharge capacity of solid solution can significantly increase, and its discharge curve presents oblique
The feature of line, without obvious discharge voltage plateau；And ternary material charge specific capacity and specific discharge capacity in this case
It can only be increased slightly, will not significantly increase, and S type features are presented in its discharge curve, there is obvious discharge voltage plateau.
Coprecipitation is to prepare the main method of ternary material.This method adds precipitating reagent the solution of mixed metal salt
In, make two or more cation co-precipitations in solution, generate precipitation mixture or solid solution presoma.Prepared by coprecipitation
Sample has the advantages that particle size distribution is narrow, tap density is high, electrochemical performance.But, coprecipitation prepare need through
Power consumption, the preparation processes of water consumption such as filtering, washing.Preparation process can produce a large amount of industrial wastewaters.In Co-precipitation
In, the precipitating reagent of addition is difficult to form uniform concentration in each several part of solution, the particle or the group of precipitation that generation precipitation is reunited
Into uneven.Further, since the precipitating concentration product difference of nickel, cobalt, manganese salt is larger, different ions deposition condition difference is larger.
Dissolution phenomena easily occurred for manganese ion in strong alkali solution so that the stoichiometric proportion of the predecessor of preparation is difficult to control, shadow
Ring the chemical property of different batches sample.
Mainly improve the performance of previously prepared ternary material by doping, Surface coating and post processing at present.However, mesh
Preceding actual improvement is unsatisfactory.At present ternary material there is a problem in that, as electronic conductivity is low, big multiplying power electric current is put
Electric stability is poor, poor, high temperature performance difference of cyclical stability etc. under high voltage.
Graphene is made up of single layer of carbon atom, is had excellent machinery, electricity, calorifics and optical characteristics, is grinding for people
Study carefully focus.In field of lithium ion battery, graphene may have larger application prospect.Such as, it is known that the electronics of graphene under normal temperature
Mobility is 0.2 × 106 cm2/ (V s), resistivity are about 10-6Ω cm, it is the minimum material of resistivity in the world so far
Expect ［ Novoselov K S, Geim A K, Morozov S V, et al., Science, 2004,306 (5296):666-
669..But, graphene preparation process easily occurs to stack phenomenon so that dispersiveness and surface in the electrolyte is wettable
Property by large effect, cause specific surface area and ionic conductivity decline Jae-Hyun Lee, Eun Kyung Lee,
Won-Jae Joo,Yamujin Jang, Dongmok et al.Wafer-Scale Growth of single-crystal
monolayer graphene on reusable hydrogen-terminated germanium[N]. Science
Exprss,2014-04-03. Chul Chung,Young-KwanKim, DollyShin, Dal-Hee Min et al. ,
Biomedical applications of graphene and graphene oxide [J].Acs Acc.Chem. Res,
2013, 46 (10):2211-2224. ］.Forefathers' research shows that graphene particles only have under dispersity, especially less than 10
Graphene competence exertion conduction, heat conduction, the outstanding performance such as machinery of layer.The inert state in grapheme material surface, chemistry are steady
Qualitative height, it is weaker with the interaction of other media, stronger Van der Waals force between graphene film be present, easily reunite.
Graphene is dispersed poor in polar solvent, limits the effect of practical application.The advantage of graphene is played, slows down graphite
The agglomeration of alkene, the dispersion stabilization of graphene is kept to be to maintain the key of efficiency.How in application graphene point is kept
Scattered validity is problem urgently to be resolved hurrily.At present, generally use is directly added into the scattered of the method improvement graphene of dispersant
Property, the dispersant of use, such as neopelex, polyvinylpyrrolidone etc..But, in actual use dispersant point
It is unsatisfactory to dissipate effect, the less stable of the graphene disperseed.
The content of the invention
In order to improve the process conditions of preparation, reduce the deficiency of preparation method, the invention provides high dispersive graphene to change
The method of kind rare earth doped nickel-cobalt-manganese ternary material property.It is characterized in that：
By graphene powder and activating agent according to mass ratio 1：(5~100）Mixing, 10 are stirred in 50~95 DEG C of temperature ranges
~100min, it is washed with deionized and removes excessive activating agent, until cleaning solution shows neutrality, the filter residue for filtering to obtain is slotting
Layer graphene.Add the wet grinding media of 5~1000 times of volumes of its volume in intercalated graphite alkene immediately, supersonic oscillations 5~
100min, make intercalated graphite alkene dispersed in wet grinding media, obtain intercalated graphite alkene solution.By intercalated graphite alkene solution with
Rare earth doped nickel-cobalt-manganese ternary material is according to volume ratio (5~1000）：1 mixing, obtains predecessor 1.By predecessor 1 less than
Under conditions of the vacuum of 1 atmospheric pressure and stirring, any temperature heating in 120~260 DEG C of sections, dry forerunner is made
Thing 2 or the method using spray drying, any temperature heating in 120~260 DEG C of sections, prepare dry predecessor 2.Will
Predecessor 2 is placed in air atmosphere, and 0.1~30 min is sintered under any sintering temperature in 880~980 DEG C of sections, before being made
Drive thing 3.Predecessor 3 is placed in air or pure oxygen atmosphere, is cooled to according to 10~50 DEG C/min speed from sintering temperature
Any temperature in 250 DEG C~430 DEG C sections, and 1~600 min is sintered at such a temperature, it is made what high dispersive graphene improved
Rare earth doped nickel-cobalt-manganese ternary material.
Described activating agent is the mixed solution of concentrated nitric acid, hydrogen peroxide and phosphoric acid, and its mass ratio formed is 65 wt%
Concentrated nitric acid：30 wt% hydrogen peroxide：85 wt% phosphoric acid=1：（0.1~0.5）：（1~5）.
Described wet grinding media is deionized water, distilled water, ethanol, acetone, methanol or formaldehyde.
Described graphene, its number of plies is in the range of 20~300 layers.
Described rare earth doped nickel-cobalt-manganese ternary material is the ternary material of doped lanthanum, cerium, praseodymium, gadolinium, scandium or ruthenium ion.
The mol ratio x of described rare earth doped nickel-cobalt-manganese ternary material, wherein nickel, cobalt, manganese, lithium, doping with rare-earth ions：
y：z：k：M meets following relation：
x：y：z：M=(0.45~0.51)：(0.15~0.20)：(0.27~0.30)：(0.01~0.05), 0.95≤k≤
1.10, and x+y+z+m=k；
Or x：y：z：M=(0.55~0.61)：(0.15~0.20)：(0.17~0.20)：(0.01~0.05), 0.95≤k≤
1.10, and x+y+z+m=k；
Or x：y：z：M=(0.75~0.81)：(0.05~0.10)：(0.07~0.10)：(0.01~0.05), 0.95≤k≤
1.10, and x+y+z+m=k.
Described doping with rare-earth ions is lanthanum, cerium, praseodymium, gadolinium, scandium or ruthenium ion.
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 25% 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.
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, prepare
Electrode material uniformity it is good, composition is uniform, has outstanding discharge performance, that particularly discharges under conditions of high current follows
Ring excellent performance, lays a good foundation for industrialization.
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
By the graphene powder of 100 layers of the number of plies with activating agent according to mass ratio 1：25 mixing, 20min is stirred at 60 DEG C, is used
Deionized water washing removes excessive activating agent, and until cleaning solution shows neutrality, the filter residue for filtering to obtain is intercalated graphite alkene.It is vertical
The ethanol medium of 50 times of volumes of its volume is added in intercalated graphite alkene, supersonic oscillations 20min, intercalated graphite alkene is existed
It is dispersed in ethanol medium, obtain intercalated graphite alkene solution.By intercalated graphite alkene solution with
LiNi0.50Co0.20Mn0.28Ce0.02O2Ternary material is according to volume ratio 100：1 mixing, obtains predecessor 1.By predecessor 1 0.01
Under conditions of the vacuum of individual atmospheric pressure and stirring, dry predecessor 2 is made in 200 DEG C of heating.Predecessor 2 is placed in air
In atmosphere, 1min is sintered at 910 DEG C, predecessor 3 is made.Predecessor 3 is placed in air atmosphere, according to 20 DEG C/min speed
Degree is cooled to 260 DEG C from 910 DEG C of sintering temperatures, and 6 min are sintered at 260 DEG C, and the doping that high dispersive graphene improves is made
Rare-earth ternary material.
Described activating agent is the mixed solution of concentrated nitric acid, hydrogen peroxide and phosphoric acid, and its mass ratio formed is 65 wt%
Concentrated nitric acid：30 wt% hydrogen peroxide：85 wt% phosphoric acid=1：0.15：2.1.
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 25% 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.
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, prepare
Electrode material uniformity it is good, composition is uniform, has outstanding discharge performance, that particularly discharges under conditions of high current follows
Ring excellent performance, lays a good foundation for industrialization.
Embodiment 2
By the graphene powder of 300 layers of the number of plies with activating agent according to mass ratio 1：100 mixing, 100min is stirred at 95 DEG C,
It is washed with deionized and removes excessive activating agent, until cleaning solution shows neutrality, the filter residue for filtering to obtain is intercalated graphite alkene.
The formaldehyde medium of 5 times of volumes of its volume is added in intercalated graphite alkene immediately, supersonic oscillations 5min, intercalated graphite alkene is existed
It is dispersed in formaldehyde medium, obtain intercalated graphite alkene solution.By intercalated graphite alkene solution with
Li1.03Ni0.51Co0.17Mn0.30Y0.05O2Ternary material is according to volume ratio 5：1 mixing, obtains predecessor 1.By predecessor 1 0.05
Under conditions of the vacuum of individual atmospheric pressure and stirring, dry predecessor 2 is made in 120 DEG C of heating.Predecessor 2 is placed in air
In atmosphere, 0.1min is sintered at 880 DEG C, predecessor 3 is made.Predecessor 3 is placed in air atmosphere, according to 50 DEG C/min's
Speed is cooled to 250 DEG C from 880 DEG C, and sinters 1min at 250 DEG C, and the rare earth doped ternary that high dispersive graphene improves is made
Material.
Described activating agent is the mixed solution of concentrated nitric acid, hydrogen peroxide and phosphoric acid, and its mass ratio formed is 65 wt%
Concentrated nitric acid：30 wt% hydrogen peroxide：85 wt% phosphoric acid=1：0.1：1.5.
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 25% 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.
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, prepare
Electrode material uniformity it is good, composition is uniform, has outstanding discharge performance, that particularly discharges under conditions of high current follows
Ring excellent performance, lays a good foundation for industrialization.
Embodiment 3
By the graphene powder of 150 layers of the number of plies with activating agent according to mass ratio 1：100 mixing, are stirred at 50 DEG C
100min, it is washed with deionized and removes excessive activating agent, until cleaning solution shows neutrality, the filter residue for filtering to obtain is intercalation
Graphene.The ethanol medium of 1000 times of volumes of its volume is added in intercalated graphite alkene immediately, supersonic oscillations 100min, is made
Intercalated graphite alkene is dispersed in ethanol medium, obtains intercalated graphite alkene solution.By intercalated graphite alkene solution with
Li0.99Ni0.61Co0.15Mn0.20Y0.03O2Ternary material is according to volume ratio 1000：1 mixing, obtains predecessor 1.Predecessor 1 is existed
Under conditions of the vacuum of 0.01 atmospheric pressure and stirring, dry predecessor 2 is made in 260 DEG C of heating.Predecessor 2 is placed in
In air atmosphere, 0.1min is sintered at 980 DEG C, predecessor 3 is made.Predecessor 3 is placed in oxygen atmosphere, according to 10 DEG C/min
Speed 300 DEG C are cooled to from 980 DEG C, and 600 min are sintered at 300 DEG C, it is dilute that the doping that high dispersive graphene improves are made
Native ternary material.
Described activating agent is the mixed solution of concentrated nitric acid, hydrogen peroxide and phosphoric acid, and its mass ratio formed is 65 wt%
Concentrated nitric acid：30 wt% hydrogen peroxide：85 wt% phosphoric acid=1：0.50：5.
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 25% 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.
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, prepare
Electrode material uniformity it is good, composition is uniform, has outstanding discharge performance, that particularly discharges under conditions of high current follows
Ring excellent performance, lays a good foundation for industrialization.
Embodiment 4
By the graphene powder of 100 layers of the number of plies with activating agent according to mass ratio 1：5 mixing, are stirred 10min at 50 DEG C, spend
Ion water washing removes excessive activating agent, and until cleaning solution shows neutrality, the filter residue for filtering to obtain is intercalated graphite alkene.Immediately
The METHANOL MEDIUM of 5 times of volumes of its volume is added in intercalated graphite alkene, supersonic oscillations 100min, makes intercalated graphite alkene in first
It is dispersed in alcohol medium, obtain intercalated graphite alkene solution.By intercalated graphite alkene solution with
Li0.97Ni0.81Co0.05Mn0.10Sc0.01O2Ternary material is according to volume ratio 100：1 mixing, obtains predecessor 1.Predecessor 1 is existed
Under conditions of the vacuum of 0.08 atmospheric pressure and stirring, dry predecessor 2 is made in 180 DEG C of heating.Predecessor 2 is placed in
In air atmosphere, 30 min are sintered at 890 DEG C, predecessor 3 is made.Predecessor 3 is placed in air atmosphere, according to 10 DEG C/min
Speed be cooled to 430 DEG C from 890 DEG C, and sinter 15 min at 430 DEG C, be made high dispersive graphene improves rare earth doped three
First material.
Described activating agent is the mixed solution of concentrated nitric acid, hydrogen peroxide and phosphoric acid, and its mass ratio formed is 65 wt%
Concentrated nitric acid：30 wt% hydrogen peroxide：85 wt% phosphoric acid=1：0.2：5.
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 25% 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.
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, prepare
Electrode material uniformity it is good, composition is uniform, has outstanding discharge performance, that particularly discharges under conditions of high current follows
Ring excellent performance, lays a good foundation for industrialization.
Embodiment 5
By the graphene powder of 80 layers of the number of plies with activating agent according to mass ratio 1：20 mixing, are stirred 26min at 70 DEG C, spend
Ion water washing removes excessive activating agent, and until cleaning solution shows neutrality, the filter residue for filtering to obtain is intercalated graphite alkene.Immediately
The medium-acetone of 50 times of volumes of its volume is added in intercalated graphite alkene, supersonic oscillations 5min, makes intercalated graphite alkene third
It is dispersed in ketone medium, obtain intercalated graphite alkene solution.By intercalated graphite alkene solution with
Li0.96Ni0.45Co0.20Mn0.30Ce0.01O2Ternary material is according to volume ratio 1000：1 mixing, obtains predecessor 1.Predecessor 1 is used
The method of spray drying prepares dry predecessor 2 in 120 DEG C.Predecessor 2 is placed in air atmosphere, in 880 DEG C of sintering
10min, predecessor 3 is made.Predecessor 3 is placed in air atmosphere, 300 are cooled to from 880 DEG C according to 20 DEG C/min speed
DEG C, and 60 min are sintered at 300 DEG C, the rare earth doped ternary material that high dispersive graphene improves is made.
Described activating agent is the mixed solution of concentrated nitric acid, hydrogen peroxide and phosphoric acid, and its mass ratio formed is 65 wt%
Concentrated nitric acid：30 wt% hydrogen peroxide：85 wt% phosphoric acid=1：0.5：5.
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 25% 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.
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, prepare
Electrode material uniformity it is good, composition is uniform, has outstanding discharge performance, that particularly discharges under conditions of high current follows
Ring excellent performance, lays a good foundation for industrialization.
Embodiment 6
By the graphene powder of 80 layers of the number of plies with activating agent according to mass ratio 1：5 mixing, are stirred 25min at 50 DEG C, spend
Ion water washing removes excessive activating agent, and until cleaning solution shows neutrality, the filter residue for filtering to obtain is intercalated graphite alkene.Immediately
The ethanol medium of 1000 times of volumes of its volume is added in intercalated graphite alkene, supersonic oscillations 10min, intercalated graphite alkene is existed
It is dispersed in ethanol medium, obtain intercalated graphite alkene solution.By intercalated graphite alkene solution and LiNi0.55Co0.20Mn0.20Y0.05O2
Ternary material is according to volume ratio 50：1 mixing, obtains predecessor 1.Method by predecessor 1 with spray drying, in 260 DEG C of preparations
Dry predecessor 2.Predecessor 2 is placed in air atmosphere, 30 min is sintered at 930 DEG C, predecessor 3 is made.By predecessor 3
It is placed in oxygen atmosphere, 300 DEG C is cooled to from 930 DEG C according to 20 DEG C/min speed, and 1min is sintered at 300 DEG C, height is made
The rare earth doped ternary material that dispersed graphite alkene improves.
Described activating agent is the mixed solution of concentrated nitric acid, hydrogen peroxide and phosphoric acid, and its mass ratio formed is 65 wt%
Concentrated nitric acid：30 wt% hydrogen peroxide：85 wt% phosphoric acid=1：0.15：1.5.
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 25% 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.
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, prepare
Electrode material uniformity it is good, composition is uniform, has outstanding discharge performance, that particularly discharges under conditions of high current follows
Ring excellent performance, lays a good foundation for industrialization.
Embodiment 7
By the graphene powder of 20 layers of the number of plies with activating agent according to mass ratio 1：20 mixing, 100min is stirred at 85 DEG C, is used
Deionized water washing removes excessive activating agent, and until cleaning solution shows neutrality, the filter residue for filtering to obtain is intercalated graphite alkene.It is vertical
The deionized water medium of 100 times of volumes of its volume is added in intercalated graphite alkene, supersonic oscillations 50min, makes intercalation stone
Black alkene is dispersed in deionized water medium, obtains intercalated graphite alkene solution.By intercalated graphite alkene solution with
Li1.05Ni0.80Co0.10Mn0.10Pr0.05O2Ternary material is according to volume ratio 10：1 mixing, obtains predecessor 1.By the spray of predecessor 1
The method that mist is dried prepares dry predecessor 2 in 260 DEG C.Predecessor 2 is placed in air atmosphere, sintered at 900 DEG C
10min, predecessor 3 is made.Predecessor 3 is placed in air atmosphere, 300 are cooled to from 900 DEG C according to 10 DEG C/min speed
DEG C, and 5 min are sintered at 300 DEG C, the rare earth doped ternary material that high dispersive graphene improves is made.
Described activating agent is the mixed solution of concentrated nitric acid, hydrogen peroxide and phosphoric acid, and its mass ratio formed is 65 wt%
Concentrated nitric acid：30 wt% hydrogen peroxide：85 wt% phosphoric acid=1：0.12：5.
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 25% 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.
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, prepare
Electrode material uniformity it is good, composition is uniform, has outstanding discharge performance, that particularly discharges under conditions of high current follows
Ring excellent performance, lays a good foundation for industrialization.
Claims (8)
1. the method that high dispersive graphene improves rare earth doped nickel-cobalt-manganese ternary material property, it is characterised in that：By graphene
Powder is with activating agent according to mass ratio 1：（5~100）Mixing, 10~100min is stirred in 50~95 DEG C of temperature ranges, is used
Deionized water washing removes excessive activating agent, and until cleaning solution shows neutrality, the filter residue for filtering to obtain is intercalated graphite alkene；It is vertical
The wet grinding media of 5~1000 times of volumes of its volume is added in intercalated graphite alkene, 5~100min of supersonic oscillations, makes to insert
Layer graphene is dispersed in wet grinding media, obtains intercalated graphite alkene solution；By intercalated graphite alkene solution with it is rare earth doped
Nickel-cobalt-manganese ternary material is according to volume ratio（5~1000）：1 mixing, obtains predecessor 1；By predecessor 1 in less than 1 atmospheric pressure
Under conditions of the vacuum of power and stirring, any temperature heating in 120~260 DEG C of sections, the predecessor 2 of drying is made or adopts
With the method for spray drying, any temperature heating in 120~260 DEG C of sections, dry predecessor 2 is prepared；Predecessor 2 is put
In air atmosphere, 0.1~30 min is sintered under any sintering temperature in 880~980 DEG C of sections, predecessor 3 is made；By before
Drive thing 3 to be placed in air or oxygen atmosphere, 250 DEG C~430 DEG C areas are cooled to from sintering temperature according to 10~50 DEG C/min speed
Between any temperature, and sinter 1~600 min at such a temperature, the rare earth doped nickel cobalt that high dispersive graphene improves be made
Manganese ternary material；
Described activating agent is the mixed solution of concentrated nitric acid, hydrogen peroxide and phosphoric acid, and its mass ratio formed is the dense nitre of 65 wt%
Acid：30 wt% hydrogen peroxide：85 wt% phosphoric acid=1：（0.1~0.5）：（1~5）.
2. the method that high dispersive graphene according to claim 1 improves rare earth doped nickel-cobalt-manganese ternary material property,
It is characterized in that described wet grinding media is deionized water, distilled water, ethanol, acetone, methanol or formaldehyde.
3. the method that high dispersive graphene according to claim 1 improves rare earth doped nickel-cobalt-manganese ternary material property,
It is characterized in that described graphene, its number of plies is in the range of 20~300 layers.
4. the method that high dispersive graphene according to claim 1 improves rare earth doped nickel-cobalt-manganese ternary material property,
It is characterized in that in described nickel-cobalt-manganese ternary material, nickel, cobalt, manganese, lithium, the mol ratio x of doping with rare-earth ions：y：z：k：m
Meet following relation：x：y：z：m =（0.45~0.51）：（0.15~0.20）：（0.27~0.30）：（0.01~0.05）,
0.95≤k≤1.10, and x+y+z+m=k.
5. the method that high dispersive graphene according to claim 1 improves rare earth doped nickel-cobalt-manganese ternary material property,
It is characterized in that in described nickel-cobalt-manganese ternary material, nickel, cobalt, manganese, lithium, the mol ratio x of doping with rare-earth ions：y：z：k：m
Meet following relation：x：y：z：m =（0.55~0.61）：（0.15~0.20）：（0.17~0.20）：（0.01~0.05）,
0.95≤k≤1.10, and x+y+z+m=k.
6. the method that high dispersive graphene according to claim 1 improves rare earth doped nickel-cobalt-manganese ternary material property,
It is characterized in that in described nickel-cobalt-manganese ternary material, nickel, cobalt, manganese, lithium, the mol ratio x of doping with rare-earth ions：y：z：k：m
Meet following relation：x：y：z：m =（0.75~0.81）：（0.05~0.10）：（0.07~0.10）：（0.01~0.05）,
0.95≤k≤1.10, and x+y+z+m=k.
7. the method that high dispersive graphene according to claim 1 improves rare earth doped nickel-cobalt-manganese ternary material property,
It is characterized in that described doping with rare-earth ions is lanthanum, cerium, praseodymium, gadolinium, scandium or ruthenium ion.
8. the method that high dispersive graphene according to claim 1 improves rare earth doped nickel-cobalt-manganese ternary material property,
It is characterized in that described rare earth doped nickel-cobalt-manganese ternary material is the ternary material of doped lanthanum, cerium, praseodymium, gadolinium, scandium or ruthenium ion
Material.
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