CN109802111A - A kind of nickelic tertiary cathode material of rubidium element doping and its preparation method and application - Google Patents
A kind of nickelic tertiary cathode material of rubidium element doping and its preparation method and application Download PDFInfo
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- CN109802111A CN109802111A CN201811652782.1A CN201811652782A CN109802111A CN 109802111 A CN109802111 A CN 109802111A CN 201811652782 A CN201811652782 A CN 201811652782A CN 109802111 A CN109802111 A CN 109802111A
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Abstract
The invention discloses a kind of nickelic tertiary cathode material of rubidium element doping and its preparation method and application, the chemical formula of the nickelic tertiary cathode material of rubidium element doping is Li1‑ xRbxNiyCozMn1‑y‑zO2, wherein y >=0.6,0 < x <, 0.2,0 < z < 0.4.The preparation method of the nickelic tertiary cathode material of rubidium element doping includes the following steps: with taking the source Li, the source Rb；The source Mn, the source Co, the source Ni, mixing obtains mixture, nitric acid is added into mixture until mixture dissolution obtains mixed liquor, chelating agent is added in reaction, obtain gel, dry acquisition presoma, presoma are pre-sintered under oxygen atmosphere after grinding for the first time, cooling second of grinding, then high temperature sintering is carried out to get the nickelic tertiary cathode material of rubidium element doping.The nickelic tertiary cathode material particle of rubidium element doping of the present invention is uniform, has micro-nano size, cationic mixing degree low, is used for lithium ion battery, specific discharge capacity is high, and high rate performance is high, good cycle, long service life.
Description
Technical field
The present invention relates to a kind of nickelic tertiary cathode materials of rubidium element doping and its preparation method and application, belong to lithium ion
Cell positive material application field.
Background technique
Nowadays, lithium ion battery (LIBs) is because of its high-energy density, good cyclicity and original environment friendly
The advantages that and be widely used in portable electronic device, and to electric car application field develop.But with portable electronics
The development of the function enhancing and electric car of electric appliance, energy density, stability and the high rate performance of lithium ion battery increasingly cannot
Meet everybody needs.Therefore, the lithium ion battery of high-energy density, high circulation stability and high rate capability is researched and developed to alleviation
Energy shortage, improves environment, and developing national economy and safeguarding national security is of great significance.
The positive electrode of lithium ion battery be restrict battery capacity and cyclical stability key factor, it determine lithium from
The characteristic and price of sub- battery are the core and key of lithium ion battery technology, and restrict lithium ion battery large-scale promotion
The key of application.Nowadays common anode material for lithium-ion batteries is LiCoO2、LiMnO2/LiMn2O4、LiMePO4、
LiNixCoyAlzO2)(NCA)、LiNixCoyMnzO2(NCM).Wherein nickelic ternary NCM due to its specific capacity is high, have extended cycle life,
The advantages that having a safety feature, is cheap is considered as optimal positive electrode.
The mainstream selection for the anode material for lithium ion battery being commercialized at present is ternary material NCM.But since cobalt is
Expensive scarce resource limits a large amount of uses of the cobalt in positive electrode preparation, while the raising of nickel content can increase
Add the specific capacity of tertiary cathode material, so nickelic tertiary cathode material becomes inevitable choice.But nickelic ternary material
In there are oxygen defects and lithium nickel mixing phenomenon, and the material is sensitive to ambient humidity, more demanding to synthesis condition, prepares difficulty
It is larger.Furthermore the first circle efficiency for charge-discharge of tertiary cathode material is lower, limits further increasing for specific capacity.So nickelic three
First positive electrode applies the upper space still to make progress in productionization, and there are also problems demand solutions.
Currently, a kind of main stream approach for improving tertiary cathode material NCM chemical property is to carry out element doping.Commonly
Doped ions are several unit prices and multivalence foreign cation, such as Ag+、Na+、Co2+、Cu2+、Mg2+、Zn2+、Ba2+、Al3+、Fe3+、Cr3 +、Ga3+、Zr4+、Ti4+Deng and some nonmetallic ions (boron, fluorine).For example, Mg and Zn are most common+divalent doped chemicals,
Being doped into NCM can be such that material specific capacity is declined slightly later, but cycle life can greatly improve；Cr is relatively conventional+trivalent
Doped chemical, research finds that suitable doping can inhibit cationic mixing phenomenon, to improve specific capacity and cycle life；Ti
It is+4 valence elements, the variation of valence being not involved in material charge and discharge, but stabilizing material structural improvement material circulation can be passed through
Performance.
But above-described element doping modified method be all to polyhedral structure element doping in layer, i.e., to Ni, Co,
The doping of the position Mn, and doping effect is undesirable, can only make battery performance slightly improves or even to sacrifice certain performance
Another performance can be made to increase, be difficult have larger help to production practices application.
Summary of the invention
In view of the deficiencies of the prior art, the first purpose of this invention is to provide that a kind of particle is uniform, has micro-nano ruler
A kind of low nickelic tertiary cathode material of rubidium element doping of very little, cationic mixing degree.
Second object of the present invention is to provide a kind of preparation method of nickelic tertiary cathode material of rubidium element doping.
Third object of the present invention is to provide a kind of application of nickelic tertiary cathode material of rubidium element doping, will be nickelic
Tertiary cathode material is applied to lithium ion battery, and gained lithium ion battery specific discharge capacity is high, and high rate performance is high, cycle performance
It is good, long service life.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of nickelic tertiary cathode material of rubidium element doping of the present invention, the nickelic tertiary cathode material of rubidium element doping
Chemical formula is Li1-xRbxNiyCozMn1-y-zO2, wherein y >=0.6,0 < x <, 0.2,0 < z < 0.4.
Preferred scheme, the chemical formula of the nickelic tertiary cathode material of rubidium element doping are Li1-xRbxNiyCozMn1-y- zO2, wherein y >=0.6,0 < x <, 0.1,0 < z < 0.4.
As a further preference, the chemical formula of the nickelic tertiary cathode material of rubidium element doping is Li1- xRbxNiyCozMn1-y-zO2, wherein y >=0.6,0 < x <, 0.05,0 < z < 0.4.
As further preferably, the chemical formula of the nickelic tertiary cathode material of rubidium element doping is Li1- xRbxNiyCozMn1-y-zO2, wherein y >=0.6,0 < x <, 0.01,0 < z < 0.4.
Technical solution of the present invention, provides a kind of nickelic tertiary cathode material of rubidium element doping, and the material passes through Li
Position doping obtains, that is, is directed to the doping vario-property of interlayer ion, using the biggish atomic size of alkali metal ion rubidium (Rb), increases
The interlamellar spacing of crystal, so that the ability of the removal lithium embedded of positive electrode is improved, enhancing storage lithium performance and charging and discharging capabilities.
The chemical formula of preferred scheme, the nickelic tertiary cathode material of rubidium element doping is,
Li0.995Rb0.005Ni0.6Co0.2Mn0.2O2、Li0.99Rb0.01Ni0.6Co0.2Mn0.2O2、Li0.97Rb0.03Ni0.6Co0.2Mn0.2O2、
Li0.95Rb0.05Ni0.6Co0.2Mn0.2O2、Li0.9Rb0.1Ni0.6Co0.2Mn0.2O2In any one.
As a further preference, the chemical formula of the nickelic tertiary cathode material of rubidium element doping is,
Li0.995Rb0.005Ni0.6Co0.2Mn0.2O2Or Li0.99Rb0.01Ni0.6Co0.2Mn0.2O2。
As a further preference, the chemical formula of the nickelic tertiary cathode material of rubidium element doping is,
Li0.995Rb0.005Ni0.6Co0.2Mn0.2O2。
Preferred scheme, the partial size of the nickelic tertiary cathode material of rubidium element doping are 1-5 μm.
Preferred scheme, the nickelic tertiary cathode material of rubidium element doping are prepared by sol-gal process.
A kind of preparation method of the nickelic tertiary cathode material of rubidium element doping of the present invention includes the following steps: with taking the source Li,
The source Rb；The source Mn, the source Co, the source Ni, mixing obtain mixture, nitric acid solution are added into mixture, so that mixture dissolution obtains
Mixed liquor, reaction, addition chelating agent obtain gel, dry to obtain presoma, after presoma grinding for the first time under oxygen atmosphere
It is pre-sintered, then cooling second of grinding carries out high temperature sintering under oxygen atmosphere to get the nickelic ternary of rubidium element doping
Positive electrode.
What the present invention initiated has prepared the nickelic tertiary cathode material of rubidium element doping by sol-gal process, by molten
Sol-gel, can obtain particle diameter distribution uniformly, the nickelic tertiary cathode material of rubidium element doping of micro-nano size.
During each raw material is with taking, wherein the source Mn, the source Co, the source Ni is matched by the design proportion of chemical formula to be taken.
Preferred scheme, in the mixture, according to the molar ratio, the integral molar quantity (Li+Rb) of Li element, Rb element: Mn
Element, Co element, Ni element integral molar quantity (Mn+Co+Ni)=1.02-1.06:1.
The additional amount in the source Li and rubidium source must be controlled effectively in the present invention, and Li element, the integral molar quantity of Rb element are opposite
It needs to slightly have excessively in the integral molar quantity of Mn element, Co element, Ni element, otherwise will cause element missing, make under battery performance
Drop.
As a further preference, in the mixture, according to the molar ratio, (Li+Rb): (Mn+Co+Ni)=1.04-
1.05:1。
Preferred scheme, in the mixture, according to the molar ratio, Rb:Li=0.001-0.2:0.8-0.999.
As a further preference, in the mixture, according to the molar ratio, Rb:Li=0.005-0.1:0.09-0.995
As it is further preferably, in the mixture, according to the molar ratio, Rb:Li=0.005-0.01:0.99-
0.995。
Inventors have found that the doping of rubidium is very big on the influence of the performance of material, if doping is too small, to material crystalline substance
Lattice parameter influences little；Improved effect is not had, if doping is excessive, the resistance of material can be made excessive, to make material
Electric property deteriorate.When rubidium doping is 0.5%-1%, the performance of resulting materials is more excellent, and especially doping is 0.5%
When, the performance of resulting materials is best.
Preferred scheme, the source Li are selected from LiOH, CH3COOLi, Li2CO3At least one of.
Preferred scheme, the source Rb are selected from RbOH, Rb2CO3At least one of.
Preferred scheme, the source Ni in nickel nitrate, nickel chloride, nickelous carbonate, nickel sulfate, nickel acetate at least one
Kind, the source Co is selected from least one of cobalt nitrate, cobalt chloride, cobalt carbonate, cobaltous sulfate, cobalt acetate, and the manganese source is selected from nitre
Sour manganese, at least one of manganese chloride, manganese carbonate, manganese sulfate, manganese acetate.
Preferred scheme, the mass fraction of the nitric acid solution are 65-68%.In the present invention, the nitric acid being added
Amount is only to play hydrotropy, in the actual operation process, a small amount of deionization can first be added without being precisely controlled
Then water submerged raw material is added the nitric acid dope of above-mentioned mass fraction, makes dissolution of raw material.
Preferred embodiment, the temperature of the reaction are 60~80 DEG C, and the time of reaction is 1-5h.
Preferred scheme, the intercalating agent are selected from least one of citric acid, glycine, maleic acid.
Preferred scheme, the additional amount of the intercalating agent are the nickelic tertiary cathode material quality of target product rubidium element doping
20%-200%.
As a further preference, the additional amount of the intercalating agent is the nickelic tertiary cathode material of target product rubidium element doping
Expect the 20%-30% of quality.
Preferred scheme, the adding manner of intercalating agent are as follows: intercalating agent is divided into 2~6 parts, is added in mixed liquor by several times,
It is stirred continuously in adition process, until mixed liquor is at thick, stopping stirring.
Inventors have found that having to the addition for controlling chelating agent to obtain homogeneous colloidal sol, the addition of chelating agent is needed
It to be added by several times, and need lasting stirring, the colloidal sol otherwise prepared is inhomogenous by ingredient, and battery performance deteriorates.
Preferred scheme, the temperature of the drying are 60-120 DEG C, and the dry time is 18-24h.
Preferred scheme, the time of the first time grinding are 10-30min, and the time of second of grinding is 10-30min.
Preferred scheme, the temperature of the pre-sintering are 350-500 DEG C, time 3-5h, and heating rate is 1-5 DEG C/min
Preferred scheme, the temperature of the high temperature sintering are 750-900 DEG C, time 8-20h, heating rate is 1-3 DEG C/
min。
Inventors have found that needing first to grind precursor material, mainly filling material for the effect obtained
Point dispersion needs to increase grinding steps and during two-step sintering, mainly due to being pre-sintered during, had part
Reunite, grinding is uniformly mixed material, improves sintering effect, and otherwise diffusion is uneven in sintering process, leads to product component not
Uniform, battery performance deteriorates.Grinding need to only be ground using agate in the prior art, and ball-milling technology can also be used.
In addition, during the sintering process, needing gradient sintering in two times, first sintering is primarily to make material diffusion more
Add sufficiently, make that the Material growth of high temperature sintering again is complete, crystallinity is more preferable, granularity is bigger.Meanwhile it also needing effectively to control heating
Rate, if heating rate is too fast, also if to will lead to material diffusion insufficient, cause sintered product ingredient uneven or sintered product
Structure is undesirable.
In the present invention, the cooling after the completion of two-step sintering uses natural cooling.
A kind of application of the nickelic tertiary cathode material of rubidium element doping of the present invention, just by the nickelic ternary of rubidium element doping
Pole material is applied in lithium ion battery.
The utility model has the advantages that
The present invention provides a kind of nickelic tertiary cathode material of rubidium element doping, the material is obtained by Li doping,
Increase the interlayer of crystal using the biggish atomic size of alkali metal ion rubidium (Rb) for the doping vario-property of interlayer ion
Away from, so that the ability of the removal lithium embedded of positive electrode is improved, enhancing storage lithium performance and charging and discharging capabilities.The rubidium element doping is high
Nickel ternary material, which is used as anode material for lithium-ion batteries, has cationic mixing degree low, and specific discharge capacity is high, and high rate performance is high,
The advantages that good cycle, long service life.
The nickelic tertiary cathode material of rubidium element doping of the invention is prepared using sol-gal process, it is possible to prevente effectively from
It is doped that bring granularity is coarse, particle is non-uniform asks to ternary material using high-temperature solid-phase sintering method in tradition preparation
Topic, can carry out the doping of micro/nano-scale, and material is made to have preferable pattern and particle uniformity.
The equipment that preparation method of the invention needs to use is simple, and reaction condition is simple, effectively has large-scale industry raw
The application prospect of production.
Detailed description of the invention
Fig. 1 is the XRD diagram of the nickelic ternary material electrode material of rubidium element doping prepared by embodiment 1.
Fig. 2 is the chemical property figure of the nickelic ternary material electrode material of rubidium element doping prepared in the present invention.
Specific embodiment
Embodiment 1
The target product of the present embodiment is Li0.995Rb0.005Ni6Co2Mn2O2。
Stoichiometrically weigh Li2CO3,Rb2CO3,Mn(NO3)2,CoCO3,Ni(NO3)2·6H2O, n (Li+Rb): n
(Ni+Co+Mn)=1.045, n (Rb2CO3): (Li2CO3)=0.005:0.995.It is slowly added to suitable dense HNO3(mass fraction
68%) it helps to dissolve.By the water bath with thermostatic control 2 hours of 70 DEG C of dissolved reactant, target product amount of substance 25% is added in four batches
Citric acid make intercalating agent.It is stirred continuously solution when citric acid is added, until liquid is at thick, stops stirring, generates quickly
At the cellular gel of brownish red.Gel is put into baking oven 100 DEG C of drying several hours and until being completely dried obtains target
Material precursor.It will be transferred in quartz boat after the presoma grinding 15min after drying later and be placed in formula furnace quartz ampoule center.It is right
Quartz ampoule vacuumizes and uses O2Quartz ampoule is full of by gas, and repetitive operation is three times.Adjustment gas flow is 200sccm (mark per minute
Quasi- milliliter).400 DEG C of 3h are first pre-sintered, agate is ground 10 minutes again after natural cooling, then with furnace after 860 DEG C of high temperature sintering 10h
It naturally cools to room temperature and obtains the nickelic tertiary cathode material of rubidium doping.The nickelic tertiary cathode material of gained rubidium element doping is averaged
Partial size is 3um.Particle size range is 1-5um, uniform particle sizes, narrowly distributing.
Fig. 1 gives the XRD diagram of 1 resulting materials of embodiment, and the XRD sample that this method synthesizes as the result is shown belongs to hexagonal crystal
The LiNiO of system2Crystal structure can determine that as pure single Li1-xRbxNiyCozMn1-y-zO2Ternary material.Comparison cation has
Sequence level index --- I (003)/I (104), ratio increase, it is meant that the decline of Li/Ni mixing degree, element ordering degree
It improves.
As shown in Fig. 2, under the conditions of 25 DEG C of room temperature, adulterate the NCM622 of 0.5%Rb under the current density of 1C, first circle
Specific discharge capacity is 144.3mAh/g.As can be seen that first circle specific discharge capacity promotes 40% relative to the comparative example 1 for not mixing rubidium
More than.First circle specific discharge capacity obtains significantly rising.
Embodiment 2
The target product of the present embodiment is Li0.95Rb0.05Ni6Co2Mn2O2。
Stoichiometrically weigh Li2CO3,Rb2CO3,Mn(NO3)2,CoCO3,Ni(NO3)2·6H2O, n (Li+Rb): n
(Ni+Co+Mn)=1.045, n (Rb2CO3): (Li2CO3)=0.05:0.95.It is slowly added to suitable dense HNO3Help is dissolved.It will
The water bath with thermostatic control 2 hours of 70 DEG C of dissolved reactant, the citric acid that target product amount of substance 25% is added in four batches make intercalating agent.
It is stirred continuously solution when citric acid is added, until liquid is at thick, stops stirring, it is cellular solidifying to generate into brownish red quickly
Glue.Gel is put into baking oven 100 DEG C of drying several hours and until being completely dried obtains target material precursor.It will do later
It is transferred in quartz boat after presoma grinding 15min after dry and is placed in formula furnace quartz ampoule center.Quartz ampoule is vacuumized and uses O2
Quartz ampoule is full of by gas, and repetitive operation is three times.Adjustment gas flow is 200sccm (standard milliliters per minute).First it is pre-sintered 400
DEG C 3h, agate is ground 10 minutes again after natural cooling, then is naturally cooled to room temperature with furnace after 860 DEG C of high temperature sintering 10h and obtained
Rubidium adulterates nickelic tertiary cathode material.
As shown in Fig. 2, under the conditions of 25 DEG C of room temperature, adulterate the NCM622 of 5%Rb under the current density of 1C, first circle is put
Electric specific capacity is 107.1mAh/g.
Embodiment 3
The target product of the present embodiment is Li0.90Rb0.1Ni6Co2Mn2O2。
Stoichiometrically weigh Li2CO3,Rb2CO3,Mn(NO3)2,CoCO3,Ni(NO3)2·6H2O, n (Li+Rb): n
(Ni+Co+Mn)=1.045, n (Rb2CO3): (Li2CO3)=0.1:0.9.It is slowly added to suitable dense HNO3(mass fraction
68%) it helps to dissolve.By the water bath with thermostatic control 2 hours of 70 DEG C of dissolved reactant, target product amount of substance 25% is added in four batches
Citric acid make intercalating agent.It is stirred continuously solution when citric acid is added, until liquid is at thick, stops stirring, generates quickly
At the cellular gel of brownish red.Gel is put into baking oven 100 DEG C of drying several hours and until being completely dried obtains target
Material precursor.It will be transferred in quartz boat after the presoma grinding 15min after drying later and be placed in formula furnace quartz ampoule center.It is right
Quartz ampoule vacuumizes and uses O2Quartz ampoule is full of by gas, and repetitive operation is three times.Adjustment gas flow is 200sccm (mark per minute
Quasi- milliliter).400 DEG C of 3h are first pre-sintered, agate is ground 10 minutes again after natural cooling, then with furnace after 860 DEG C of high temperature sintering 10h
It naturally cools to room temperature and obtains the nickelic tertiary cathode material of rubidium doping.
As shown in Fig. 2, under the conditions of 25 DEG C of room temperature, adulterate the NCM622 of 10%Rb under the current density of 1C, first circle
Specific discharge capacity is 117.8mAh/g.As can be seen that first circle specific discharge capacity promotes 16% relative to the comparative example 1 for not mixing rubidium
More than.
Comparative example 1
Stoichiometrically weigh Li2CO3,Mn(NO3)2,CoCO3,Ni(NO3)2·6H2O, n (Li): n (Ni+Co+Mn)=
1.045:1.It is slowly added to suitable dense HNO3(mass fraction 68%) help is dissolved.By 70 DEG C of constant temperature of dissolved reactant
Water-bath 2 hours, the citric acid that target product amount of substance 25% is added in four batches made intercalating agent.It is stirred continuously when citric acid is added molten
Liquid stops stirring, generates into the cellular gel of brownish red quickly until liquid is at thick.Gel is put into 100 in baking oven
DEG C dry several hours obtain target material precursor until being completely dried.The presoma after drying is ground into 15min later
After be transferred in quartz boat and be placed in formula furnace quartz ampoule center.Quartz ampoule is vacuumized and uses O2Quartz ampoule is full of by gas, repeats to grasp
Make three times.Adjustment gas flow is 200sccm (standard milliliters per minute).400 DEG C of 3h are first pre-sintered, agate again after natural cooling
Room temperature, which is naturally cooled to, with furnace after grinding 10 minutes, then 860 DEG C of high temperature sintering 10h obtains the nickelic tertiary cathode material of rubidium doping
Material.
As shown in Fig. 2, the NCM622 to undope is under the current density of 1C, first circle electric discharge ratio under the conditions of 25 DEG C of room temperature
Capacity is 101.8mAh/g.
Comparative example 2
Stoichiometrically weigh Li2CO3,Mn(NO3)2,CoCO3,Ni(NO3)2·6H2O, n (Li): n (Ni+Co+Mn)=
1.045:1, n (Rb2CO3)/(Li2CO3)=0.005:0.995 is slowly added to suitable dense HNO3 (mass fraction 68%) and helps
Dissolution.By the water bath with thermostatic control 2 hours of 70 DEG C of dissolved reactant, the citric acid that target product amount of substance 25% is added in four batches is made
Intercalating agent.It is stirred continuously solution when citric acid is added, until liquid is at thick, stops stirring, generates into brownish red bee quickly
The gel of nest shape.Gel is put into baking oven 100 DEG C of drying several hours and until being completely dried obtains target material precursor.
It will be transferred in quartz boat after the presoma grinding 15min after drying later and be placed in formula furnace quartz ampoule center.Quartz ampoule is taken out true
Quartz ampoule is simultaneously full of with O2 gas by sky, and repetitive operation is three times.Adjustment gas flow is 200sccm (standard milliliters per minute).First
400 DEG C of 3h are pre-sintered, it is not ground, then with furnace naturally cool to room temperature after 860 DEG C of high temperature sintering 10h to obtain rubidium doping nickelic
Tertiary cathode material.
As a result NCM622 obtained is not ground during double sintering, battery performance is very poor, can only recycle 3-4 circle.
Comparative example 3
Other conditions are identical as the embodiment of the present invention 1, only non-gradient increased temperature, but go straight up to 860 DEG C of heat preservation sinterings, as a result
The product obtained after being sintered, it is uneven particle equally occur, and it is bad finally to measure chemical property.
Comparative example 4
Other conditions are identical as the embodiment of the present invention 1, are only the heating rates that sintering process is all made of 10 DEG C/min, as a result
The product obtained after being sintered, it is uneven particle equally occur, and it is bad finally to measure chemical property.
Claims (10)
1. a kind of nickelic tertiary cathode material of rubidium element doping, it is characterised in that: the nickelic tertiary cathode material of rubidium element doping
The chemical formula of material is Li1-xRbxNiyCozMn1-y-zO2, wherein y >=0.6,0 < x <, 0.2,0 < z < 0.4.
2. a kind of nickelic tertiary cathode material of rubidium element doping according to claim 1, it is characterised in that: the rubidium element
The partial size for adulterating nickelic tertiary cathode material is 1-5um.
3. preparing a kind of method of the nickelic tertiary cathode material of rubidium element doping as claimed in claim 1 or 2, feature exists
In including the following steps: with taking the source Li, the source Rb；The source Mn, the source Co, the source Ni, mixing obtain mixture, nitre are added into mixture
Acid solution, so that mixture dissolution obtains mixed liquor, chelating agent is added in reaction, obtains gel, dry to obtain presoma, forerunner
Body is pre-sintered under oxygen atmosphere after grinding for the first time, then cooling second of grinding carries out high temperature under oxygen atmosphere
Sintering is to get the nickelic tertiary cathode material of rubidium element doping.
4. a kind of preparation method of nickelic tertiary cathode material of rubidium element doping according to claim 3, it is characterised in that:
In the mixture, according to the molar ratio, (Li+Rb): (Mn+Co+Ni)=1.02-1.06:1.
5. a kind of preparation method of nickelic tertiary cathode material of rubidium element doping according to claim 3, it is characterised in that:
In the mixture, according to the molar ratio, Rb:Li=0.001-0.2:0.8-0.999.
6. a kind of preparation method of nickelic tertiary cathode material of rubidium element doping according to claim 3, it is characterised in that:
The source Li is selected from LiOH, CH3COOLi、Li2CO3At least one of；
The source Rb is selected from RbOH, Rb2CO3At least one of；
The source Ni is selected from least one of nickel nitrate, nickel chloride, nickelous carbonate, nickel sulfate, nickel acetate, and the source Co is selected from nitre
At least one of sour cobalt, cobalt chloride, cobalt carbonate, cobaltous sulfate, cobalt acetate, the manganese source be selected from manganese nitrate, manganese chloride, carbonic acid
At least one of manganese, manganese sulfate, manganese acetate.
7. a kind of preparation method of nickelic tertiary cathode material of rubidium element doping according to claim 3, it is characterised in that:
The temperature of the reaction is 60~80 DEG C, and the time of reaction is 1-5h.
8. a kind of preparation method of nickelic tertiary cathode material of rubidium element doping according to claim 3, it is characterised in that:
The intercalating agent is selected from least one of citric acid, glycine, maleic acid；
The additional amount of the intercalating agent is the 20%-200% of the nickelic tertiary cathode material quality of target product rubidium element doping；
The adding manner of intercalating agent are as follows: intercalating agent is divided into 2~6 parts, is added in mixed liquor, is constantly stirred in adition process by several times
It mixes, until mixed liquor is at thick, stopping stirring.
9. a kind of preparation method of nickelic tertiary cathode material of rubidium element doping according to claim 3, it is characterised in that:
The temperature of the pre-sintering is 350-500 DEG C, time 3-5h, and heating rate is 1-5 DEG C/min, the temperature of the high temperature sintering
It is 750-900 DEG C, time 8-20h, heating rate is 1-3 DEG C/min.
10. a kind of application of the nickelic tertiary cathode material of rubidium element doping described in any one according to claim 1~2,
It is characterized in that: the nickelic tertiary cathode material of rubidium element doping is applied in lithium ion battery.
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| CN111490244A (en) * | 2020-06-02 | 2020-08-04 | 金国辉 | Nano lithium zirconate coated potassium-doped nickel cobalt lithium manganate positive electrode material and preparation method thereof |
| CN114804233A (en) * | 2022-05-17 | 2022-07-29 | 无锡零一未来新材料技术研究院有限公司 | High-nickel ternary cathode material for lithium battery and preparation method thereof |
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| CN111490244A (en) * | 2020-06-02 | 2020-08-04 | 金国辉 | Nano lithium zirconate coated potassium-doped nickel cobalt lithium manganate positive electrode material and preparation method thereof |
| CN114804233A (en) * | 2022-05-17 | 2022-07-29 | 无锡零一未来新材料技术研究院有限公司 | High-nickel ternary cathode material for lithium battery and preparation method thereof |
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