CN107611400A - The method that high dispersive graphene improves nickel-cobalt-manganese ternary material electrochemical performance - Google Patents
The method that high dispersive graphene improves nickel-cobalt-manganese ternary material electrochemical performance Download PDFInfo
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Abstract
The present invention relates to the method that high dispersive graphene improves nickel-cobalt-manganese ternary material electrochemical performance, it is characterised in that：Graphene powder is mixed with activating agent, by being stirred, washing, the step such as filtering intercalated graphite alkene is made.Predecessor is prepared by humidifying grinding media, mixing ternary material, drying and other steps.Predecessor is placed in air atmosphere, through oversintering, cooling, the nickel-cobalt-manganese ternary material that high dispersive graphene improves is made in the step such as sintering again.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 that the high dispersive graphene of polymer battery and ultracapacitor improves nickel-cobalt-manganese ternary material electrochemical performance.
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 nickel-cobalt-manganese ternary material electrochemical performance, preparation method is overcome the shortcomings of, the present invention uses high dispersive
Graphene is used for the chemical property for improving nickel-cobalt-manganese ternary material.It is characterized in that：
By graphene powder and activating agent according to mass ratio 1：(5~100）Mixing, 10 are stirred in 40~95 DEG C of temperature ranges
~100min.It is washed with deionized until cleaning solution shows neutrality, the filter residue for filtering to obtain is intercalated graphite alkene.Inserting immediately
The wet grinding media of 5~1000 times of volumes of its volume is added in layer graphene, 5~100min of supersonic oscillations, makes intercalated graphite
Alkene is dispersed in wet grinding media, obtains intercalated graphite alkene solution.Intercalated graphite alkene solution and nickel-cobalt-manganese ternary material are pressed
According to volume ratio (5~100）：1 mixing, obtains predecessor 1.By predecessor 1 under the vacuum condition less than 1 atmospheric pressure, in
Any temperature heating in 130~270 DEG C of sections, is made dry predecessor 2, or the method using spray drying, in 130~
Any temperature heating in 270 DEG C of sections, prepares dry predecessor 2.Predecessor 2 is placed in air atmosphere, 800~950
Any sintering temperature in DEG C section sinters 0.1~300 min, and predecessor 3 is made.Predecessor 3 is placed in air or pure oxygen atmosphere
In, any temperature in 200~450 DEG C of sections is cooled to from sintering temperature according to 1~50 DEG C/min speed, and in the temperature
The nickel-cobalt-manganese ternary material that high dispersive graphene improves is made in 1~600 min of lower sintering.
Described activating agent is the mixed solution of concentrated nitric acid, hydrogen peroxide and phosphoric acid, and its mass ratio formed is 68 wt%
Concentrated nitric acid：30 wt% hydrogen peroxide：85 wt% phosphoric acid=1：（0.1~0.5）：（1~4）.
Described wet grinding media is deionized water, distilled water, ethanol, acetone, methanol or formaldehyde.
The number of plies of graphene is in the range of 3~1000 layers in described graphene powder.
The mol ratio x of nickel, cobalt, manganese, lithium in described ternary material：y：z：K meets following relation：
x：y：Z=(0.45~0.51)：(0.17~0.20)：(0.27~0.30), 0.95≤k≤1.10, and x+y+z
= k；
Or x：y：Z=(0.55~0.61)：(0.17~0.20)：(0.17~0.20), 0.95≤k≤1.10, and x+y+
z = k；
Or x：y：Z=(0.75~0.81)：(0.07~0.10)：(0.07~0.10), 0.95≤k≤1.10, and x+y+
z = k。
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 30 layers of the number of plies with activating agent according to mass ratio 1：15 mixing, are stirred 50min, then use at 85 DEG C
Deionized water washing shows neutrality until cleaning solution, and the filter residue for filtering to obtain is intercalated graphite alkene.Immediately in intercalated graphite alkene
The ethanol of 50 times of volumes of its volume is added, supersonic oscillations 50min, makes intercalated graphite alkene dispersed in ethanol, obtains
Intercalated graphite alkene solution.By intercalated graphite alkene solution and LiNi0.50Co0.20Mn0.30O2Ternary material is according to volume ratio 10：1 is mixed
Close, obtain predecessor 1.Predecessor 1 is heated under the vacuum condition of 0.01 atmospheric pressure in 180 DEG C, before being made dry
Drive thing 2.Predecessor 2 is placed in air atmosphere, 5min is sintered at 900 DEG C, predecessor 3 is made.Predecessor 3 is placed in air
In atmosphere, 300 DEG C are cooled to from 900 DEG C according to 20 DEG C/min speed, and 10 min are sintered at 300 DEG C, high dispersive is made
The ternary material that graphene improves.
Described activating agent is the mixed solution of concentrated nitric acid, hydrogen peroxide and phosphoric acid, and its mass ratio formed is 68 wt%
Concentrated nitric acid：30 wt% hydrogen peroxide：85 wt% phosphoric acid=1：0.2：1.5.
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 2
By by the graphene powder of 3 layers of the number of plies with activating agent according to mass ratio 1：5 mixing, are stirred 10min, then use at 40 DEG C
Deionized water washing shows neutrality until cleaning solution, and the filter residue for filtering to obtain is intercalated graphite alkene.Immediately in intercalated graphite alkene
The METHANOL MEDIUM of 5 times of volumes of its volume is added, supersonic oscillations 5min, intercalated graphite alkene is uniformly divided in METHANOL MEDIUM
Dissipate, obtain intercalated graphite alkene solution.By intercalated graphite alkene solution and LiNi0.60Co0.20Mn0.20O2Ternary material is according to volume ratio
5：1 mixing, obtains predecessor 1.Predecessor 1 is heated under the vacuum condition of 0.9 atmospheric pressure in 130 DEG C, drying is made
Predecessor 2.Predecessor 2 is placed in air atmosphere, 0.1min is sintered at 800 DEG C, predecessor 3 is made.Predecessor 3 is placed in
In oxygen atmosphere, 200 DEG C are cooled to from 800 DEG C according to 50 DEG C/min speed, and 1min is sintered at 200 DEG C, high dispersive is made
The ternary material that graphene improves.
Described activating agent is the mixed solution of concentrated nitric acid, hydrogen peroxide and phosphoric acid, and its mass ratio formed is 68 wt%
Concentrated nitric acid：30 wt% hydrogen peroxide：Mass ratio=1 of 85 wt% phosphoric acid：0.1：1.
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 3
By by the graphene powder of 1000 layers of the number of plies with activating agent according to mass ratio 1：100 mixing, are stirred at 95 DEG C
100min, then be washed with deionized until cleaning solution shows neutrality, the filter residue for filtering to obtain is intercalated graphite alkene.Inserting immediately
The ethanol medium of 1000 times of volumes of its volume is added in layer graphene, supersonic oscillations 100min, makes intercalated graphite alkene in second
It is dispersed in alcohol medium, obtain intercalated graphite alkene solution.By intercalated graphite alkene solution and LiNi0.80Co0.10Mn0.10O2Ternary
Material is according to volume ratio 100：1 mixing, obtains predecessor 1.By predecessor 1 under the vacuum condition less than 0.1 atmospheric pressure,
Dry predecessor 2 is made in 270 DEG C of heating.Predecessor 2 is placed in air atmosphere, 300 min is sintered at 800 DEG C, is made
Predecessor 3.Predecessor 3 is placed in air atmosphere, 200 DEG C are cooled to from 800 DEG C according to 1 DEG C/min speed, and 200
600 min are sintered at DEG C, the 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 68 wt%
Concentrated nitric acid：30 wt% hydrogen peroxide：85 wt% phosphoric acid=1：0.5：4.
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 300 layers of the number of plies with activating agent according to mass ratio 1：5 mixing, 10min is stirred at 50 DEG C.Spend
Ion water washing shows neutrality until cleaning solution, and the filter residue for filtering to obtain is intercalated graphite alkene.Add immediately in intercalated graphite alkene
Enter the medium-acetone of 50 times of volumes of its volume, supersonic oscillations 50min, intercalated graphite alkene is uniformly divided in medium-acetone
Dissipate, obtain intercalated graphite alkene solution.By intercalated graphite alkene solution and Li1.01Ni0.81Co0.10Mn0.10O2Ternary material is according to volume
Than 12：1 mixing, obtains predecessor 1.Method by predecessor 1 with spray drying, dry predecessor 2 is prepared in 130 DEG C.Will
Predecessor 2 is placed in air atmosphere, sinters 10min at 950 DEG C, predecessor 3 is made.Predecessor 3 is placed in oxygen atmosphere, according to
10 DEG C/min speed is cooled to 300 DEG C from 950 DEG C, and sinters 1min at 300 DEG C, is made high dispersive graphene improves 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 68 wt%
Concentrated nitric acid：30 wt% hydrogen peroxide：85 wt% phosphoric acid=1：0.5：3.
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 by the graphene powder of 60 layers of the number of plies with activating agent according to mass ratio 1：20 mixing, 15min is stirred at 75 DEG C, then
It is washed with deionized until cleaning solution shows neutrality, the filter residue for filtering to obtain is intercalated graphite alkene.Immediately in intercalated graphite alkene
The distillation aqueous medium of middle 10 times of volumes for adding its volume, supersonic oscillations 70min, makes intercalated graphite alkene in aqueous medium is distilled
It is dispersed, obtain intercalated graphite alkene solution.By intercalated graphite alkene solution and Li1.01Ni0.51Co0.20Mn0.30O2Ternary material is pressed
According to volume ratio 100：1 mixing, obtains predecessor 1.Method by predecessor 1 with spray drying, dry forerunner is prepared in 270 DEG C
Thing 2.Predecessor 2 is placed in air atmosphere, 5 min is sintered at 950 DEG C, predecessor 3 is made.Predecessor 3 is placed in air gas
In atmosphere, 350 DEG C are cooled to from 950 DEG C according to 5 DEG C/min speed, and 6 min are sintered at 350 DEG C, high dispersive graphite is made
The ternary material that alkene improves.
Described activating agent is the mixed solution of concentrated nitric acid, hydrogen peroxide and phosphoric acid, and its mass ratio formed is 68 wt%
Concentrated nitric acid：30 wt% hydrogen peroxide：85 wt% phosphoric acid=1：0.1：3.
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 by the graphene powder of 10 layers of the number of plies with activating agent according to mass ratio 1：90 mixing, 15 min are stirred at 65 DEG C.
It is washed with deionized until cleaning solution shows neutrality, the filter residue for filtering to obtain is intercalated graphite alkene.Immediately in intercalated graphite alkene
The formaldehyde medium of middle 8 times of volumes for adding its volume, supersonic oscillations 100min, make intercalated graphite alkene uniform in formaldehyde medium
It is scattered, obtain intercalated graphite alkene solution.By intercalated graphite alkene solution and Li1.01Ni0.61Co0.20Mn0.20O2Ternary material is according to body
Product ratio 25：1 mixing, obtains predecessor 1.Method by predecessor 1 with spray drying, dry predecessor 2 is prepared in 130 DEG C.
Predecessor 2 is placed in air atmosphere, 15min is sintered at 850 DEG C, predecessor 3 is made.Predecessor 3 is placed in air atmosphere,
450 DEG C are cooled to from 850 DEG C according to 20 DEG C/min speed, and 600 min are sintered at 450 DEG C, high dispersive graphene is made
Improved ternary material.
Described activating agent is the mixed solution of concentrated nitric acid, hydrogen peroxide and phosphoric acid, and its mass ratio formed is 68 wt%
Concentrated nitric acid：30 wt% hydrogen peroxide：85 wt% phosphoric acid=1：0.5：1.
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 7
By the graphene powder of 100 layers of the number of plies with activating agent according to mass ratio 1：100 mixing, 10min is stirred at 40 DEG C, then
It is washed with deionized until cleaning solution shows neutrality, the filter residue for filtering to obtain is intercalated graphite alkene.Immediately in intercalated graphite alkene
The deionized water medium of middle 5 times of volumes for adding its volume, supersonic oscillations 5min, makes intercalated graphite alkene in deionized water medium
In it is dispersed, obtain intercalated graphite alkene solution.By intercalated graphite alkene solution and Li0.95Ni0.75Co0.10Mn0.10O2Ternary material
According to volume ratio 5：1 mixing, obtains predecessor 1.Predecessor 1 is prepared into dry forerunner with the method for spray drying in 200 DEG C
Thing 2.Predecessor 2 is placed in air atmosphere, 300 min is sintered at 950 DEG C, predecessor 3 is made.Predecessor 3 is placed in oxygen
In atmosphere, 200 DEG C are cooled to from 950 DEG C according to 1 DEG C/min speed, and 6min is sintered at 200 DEG C, high dispersive graphite is made
The ternary material that alkene improves.
Described activating agent is the mixed solution of concentrated nitric acid, hydrogen peroxide and phosphoric acid, and its quality formed is than mass ratio
68 wt% concentrated nitric acids：30 wt% hydrogen peroxide：85 wt% phosphoric acid=1：0.1：4.
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 (6)
1. the method that high dispersive graphene improves nickel-cobalt-manganese ternary material electrochemical performance, it is characterised in that：By graphene powder
With activating agent according to mass ratio 1：(5~100）Mixing, 10~100min is stirred in 40~95 DEG C of temperature ranges;Spend from
Sub- water washing shows neutrality until cleaning solution, and the filter residue for filtering to obtain is intercalated graphite alkene;Added immediately in intercalated graphite alkene
The wet grinding media of 5~1000 times of volumes of its volume, 5~100min of supersonic oscillations, make intercalated graphite alkene in wet grinding media
It is dispersed, obtain intercalated graphite alkene solution;By intercalated graphite alkene solution and nickel-cobalt-manganese ternary material according to volume ratio (5~
100）：1 mixing, obtains predecessor 1；By predecessor 1 under the vacuum condition less than 1 atmospheric pressure, in 130~270 DEG C of areas
Between the heating of any temperature, dry predecessor 2, or the method using spray drying is made, in 130~270 DEG C of sections
Any temperature prepares dry predecessor 2;Predecessor 2 is placed in air atmosphere, any sintering in 800~950 DEG C of sections
Temperature sinters 0.1~300 min, and predecessor 3 is made;Predecessor 3 is placed in air or pure oxygen atmosphere, according to 1~50 DEG C/
Min speed is cooled to any temperature in 200~450 DEG C of sections from sintering temperature, and sinters 1~600 at such a temperature
Min, the nickel-cobalt-manganese 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 the dense nitre of 68 wt%
Acid：30 wt% hydrogen peroxide：85 wt% phosphoric acid=1：（0.1~0.5）：（1~4）.
2. the method that high dispersive graphene according to claim 1 improves nickel-cobalt-manganese ternary material electrochemical performance, it is special
Sign is 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 nickel-cobalt-manganese ternary material electrochemical performance, it is special
The number of plies in the graphene in described graphene powder is levied in the range of 3~1000 layers.
4. the method that high dispersive graphene according to claim 1 improves nickel-cobalt-manganese ternary material electrochemical performance, it is special
Levy the mol ratio x in nickel, cobalt, manganese, lithium in described ternary material：y：z：K meets following relation：x：y：Z=(0.45~
0.51)：(0.17~0.20)：(0.27~0.30), 0.95≤k≤1.10, and x+y+z=k.
5. the method that high dispersive graphene according to claim 1 improves nickel-cobalt-manganese ternary material electrochemical performance, it is special
Levy the mol ratio x in nickel, cobalt, manganese, lithium in described ternary material：y：z：K meets following relation：x：y：Z=(0.55~
0.61)：(0.17~0.20)：(0.17~0.20), 0.95≤k≤1.10, and x+y+z=k.
6. the method that high dispersive graphene according to claim 1 improves nickel-cobalt-manganese ternary material electrochemical performance, it is special
Levy the mol ratio x in nickel, cobalt, manganese, lithium in described ternary material：y：z：K meets following relation：x：y：Z=(0.75~
0.81)：(0.07~0.10)：(0.07~0.10), 0.95≤k≤1.10, and x+y+z=k.
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