CN108666559A - The carbon-coated NCA positive electrodes of N doping and lithium ion battery and preparation method - Google Patents
The carbon-coated NCA positive electrodes of N doping and lithium ion battery and preparation method Download PDFInfo
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Abstract
The present invention discloses a kind of carbon-coated NCA positive electrodes of N doping and lithium ion battery and preparation method, wherein：Carbon-coated its general structure of NCA positive electrodes of N doping is LixNi1‑y‑ zCoyAlzO2/ NC, 1≤x≤1.08,0.05 ＜ y≤0.15,0 ＜ z≤0.05, NC is nitrogen-doped carbon organic matter；LixNi1‑y‑zCoyAlzO2Positive electrode matrix：The mass ratio of NC is 100:(2~8).The present invention also provides the preparation methods of lithium ion battery and above-mentioned positive electrode using the carbon-coated NCA positive electrodes of above-mentioned N doping, the preparation method mixes nitrogenous organic carbon source with NCA positive electrodes, then the carbon-coated NCA positive electrodes of N doping are obtained by high-temperature calcination, the surface of NCA positive electrodes is coated on by nitrogen-doped carbon, contact of the positive electrode with electrolyte can be greatly reduced, nitrogen-doped carbon can also improve ternary material electronic conductivity simultaneously, improve chemical property.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries preparation fields, and in particular to a kind of carbon-coated NCA of N doping is just
Pole material and lithium ion battery and preparation method.
Technical background
Lithium ion battery is due to its high-energy density, and high working voltage, in the long circulating period, the advantages such as environmental-friendly are wide
It is general to be applied to 3C Product, electric bicycle and electric vehicle etc..With comprehensive layout new energy in various countries' in global range
The demand of electric vehicle, lithium ion battery is more and more, while requiring also increasingly the chemical property of lithium ion battery
It is high.Therefore, how to improve battery capacity and cyclical stability becomes the research emphasis of lithium ion battery.
Positive electrode is the bottleneck of lithium ion battery hoist capacity, while positive electrode accounts for the battery cost close to 1/3.
Currently, the positive electrode applied to electric vehicle is mainly ternary NCM, NCA and LiFePO4.Compared with LiFePO4, three
First material has higher energy density.Common NCM has 111 and 523 specifications currently on the market.In order to further increase ternary
The capacity of material, people begin one's study nickelic ternary material, such as NCM622, and 811, NCA etc..Wherein NCA ternary materials
(LiNi1-x-yCoxAlyO2, 0.05≤x ＜ 0.15,0≤y≤0.05), as a potential nickelic positive electrode, by each
The favor of Battery Company.
In order to improve the chemical property of ternary material, researchers are often modified processing to ternary material.Ternary
There are mainly two types of methods for the modification of material：1, it adulterates；2, surface coats, and wherein surface cladding is a kind of common industrialized changes
Property method.Such as：
Documents 1：CN106450217A (publication date 2017.02.22) discloses a kind of to tertiary cathode material progress carbon
The method of modifying of cladding, step are：Under conditions of carbon-source gas and protective gas, tertiary cathode material is sunk by gas phase
After product, carbon-coated tertiary cathode material is obtained.
Documents 2：CN103474628A (publication date 2013.12.25) discloses a kind of carbon coating tertiary cathode material
Preparation method, step are：Using nickel salt, cobalt salt and manganese salt as raw material, ternary anode material precursor is prepared；Prepare conductive carbon dispersion
System：Conductive carbon is scattered in the water containing organic carbon source；Ternary anode material precursor and lithium compound are added to and led
It in electrical carbon dispersion, is uniformly mixed, obtains mixture；Mixture is dried under vacuum；By the mixture of drying
In confined conditions or the atmosphere high temperature of inert gas shielding is handled, and obtains carbon coating tertiary cathode material.
Above-mentioned carbon-coated tertiary cathode material, due to its carbon source use be all common carbon material, cannot well every
Contact absolutely between positive electrode and electrolyte, there are still very big deficiencies for electric conductivity and chemical property.
The present invention is quasi- to provide a kind of tertiary cathode material NCA of nitrogenous carbon source cladding, to reduce positive electrode and electrolyte
Between contact, improve the electric conductivity and chemical property of positive electrode.
Invention content
The technical problem to be solved in the present invention is to provide a kind of carbon-coated NCA positive electrodes of N doping and lithium ion batteries
With preparation method.
In order to solve the above-mentioned technical problem, the present invention uses following technical scheme：
A kind of carbon-coated NCA positive electrodes of N doping, general structure Li are providedxNi1-y-zCoyAlzO2/ NC, 1≤x
≤ 1.08,0.05 ＜ y≤0.15,0 ＜ z≤0.05, NC be nitrogen-doped carbon organic matter (N-doped Carbon, hereinafter referred to as
“NC”)；
LixNi1-y-zCoyAlzO2Positive electrode matrix：The mass ratio of NC is 100:(2~8).
Further,
Above-mentioned NC is that nitrogenous Organic Compounds high-temperature calcination is formed, and the nitrogenous Organic Compounds are specially second
Ethylenediamine tetraacetic acid (EDTA) (ethylenediaminetetraacetic acid), polyvinylpyrrolidone (abbreviation PVP), one kind in polyacrylonitrile (abbreviation PAN) or pantothenic acid
Or several combination.
The present invention also provides the lithium ion battery for including the carbon-coated NCA positive electrodes of above-mentioned N doping, the lithium ions
Battery includes：Anode, cathode, diaphragm and electrolyte, it is that above-mentioned nitrogen-doped carbon coats to constitute the positive electrode in the anode
NCA positive electrodes.
The present invention also provides the preparation methods of the carbon-coated NCA positive electrodes of above-mentioned N doping, specifically include following steps：
S1, presoma is prepared：Prepare NCA ternary material precursors Ni1-y-zCoyAlz(OH)2, 0.05 ＜ y≤0.15,0 ＜ z
≤0.05；
S2, NCA positive electrode matrixes are prepared：By presoma Ni1-y-zCoyAlz(OH)2With LiOHH2O is according to molar ratio
1:(1~1.08) weighs presoma, the LiOHH of corresponding amount2O is calcined under oxidizing atmosphere after mixing, calcining
700~850 DEG C of temperature, 20~30h of calcination time；NCA positive electrode matrixes are obtained after cooling, crushing, sieving；
S3, washing：NCA positive electrodes matrix is subjected to washing and reduces residual alkali, the mass ratio of water and NCA matrixes be (0.3~
5):1, it filters, drying；
S4, the carbon-coated NCA positive electrodes of N doping are prepared：By after step S3 washing NCA positive electrodes matrix with contain
The mass ratio of the Organic Compounds of nitrogen is 100:(2~8) weigh the matrix of corresponding amount, nitrogenous Organic Compounds, mixing
After uniformly, calcined under an inert atmosphere, 600~800 DEG C, 2~4h of calcination time of calcination temperature, in high-temperature burning process,
Nitrogenous Organic Compounds formation nitrogen-doped carbon (NC) is uniformly coated on NCA ternary materials surface and is to get general structure
LixNi1-y-zCoyAlzO2The carbon-coated NCA positive electrodes of N doping of/NC, wherein：1≤x≤1.08,0.05 ＜ y≤0.15,0
Z≤0.05 ＜.
Further, presoma Ni in step S11-y-zCoyAlz(OH)2Prepare it is specific as follows：
Using the sulfate of Ni, Co, Al or nitrate as raw material, according to the amount ratio of the substance of each element in target product, i.e.,
nNi:nCo:nAl=(1-y-z):y:Z is accurately weighed and and is configured to 1~3molL-1Sulfate/nitrate mixed solution,
With 2~6molL-1NaOH be precipitating reagent, 1~3molL-1NH3·H2O is complexing agent, by sodium hydroxide and NH3·H2O into
Row is mixed to get lye and is first stirred deionized water as bottom liquid before reaction starts, is then added dropwise to mixed salt solution
In the liquid of bottom, while lye is added, the flow velocity of lye is regulated and controled with the variation of pH, and salting liquid and lye are formed in beaker
Precipitation, precipitation is washed, is dried to obtain presoma Ni1-y-zCoyAlz(OH)2。
Further,
In step S4, above-mentioned NC is that nitrogenous Organic Compounds high-temperature calcination is formed, the nitrogenous organic carbon chemical combination
Object is specially ethylenediamine tetra-acetic acid (ethylenediaminetetraacetic acid), polyvinylpyrrolidone (abbreviation PVP), polyacrylonitrile (abbreviation PAN) or general
The combination of one or more of acid.
Further,
In step S4, inert atmosphere is nitrogen atmosphere or argon gas atmosphere.
Further,
The method further includes step S5：Anode is made in the carbon-coated NCA positive electrodes of N doping made from step S4
Piece, together with negative plate, diaphragm, electrolyte, according to positive shell-positive plate-diaphragm-electrolyte-negative plate-anode coat
Sequence carries out assembling obtained lithium ion battery.
Further, step S5 specifically comprises the following steps：
S51, pyrrolidone is given a tongue-lashing using N- methyl as solvent, step S4 is made nitrogen-doped carbon cladding NCA positive electrodes and gathered partially
Vinyl fluoride and conductive black are 8 according to the amount ratio of substance:1:1 weigh after be added there is N- methyl to give a tongue-lashing in the small reagent bottle of pyrrolidone,
Carrying out magnetic agitation makes it be uniformly mixed, and obtains mixed slurry；
S52, then, by mixed slurry configure uniformly coated on aluminium foil, then dries 10 at 70~90 DEG C
~14h obtains positive plate, then punches and a diameter of 11mm positive plates are made, positive plate is weighed to calculate the matter of positive electrode
Positive plate, is then compacted on tablet press machine with the power of 35~45MPa by amount；
S53, in vacuum glove box, the positive plate after the compacting prepared with step S52 is anode, and lithium metal is cathode,
The porous polyethylene films of Celgard2400 are diaphragm, using the LiPF6/EC+DMC+EMC of 1mol/L as electrolyte, in electrolyte, and EC：
DMC：The volume ratio of EMC is 1:1:1；According to the sequence of positive shell-positive plate-diaphragm-electrolyte-negative plate-anode coat
It is assembled, obtains CR2025 button cells.
Beneficial effects of the present invention：
The present invention and side disclosed in previous carbon coating ternary material patent document (CN106450217A, CN103474628A)
Case is compared, and maximum difference is that it be in the surface coated of tertiary cathode material is a kind of carbon material of situ Nitrogen Doping,
The organic carbon source itself that it is used contains nitrogen, when high-temperature process, nitrogen can be orderly while generating carbon material distribution
In the lattice of carbon material.In contrast, separated carbon source carries out at high temperature again after mixing with nitrogen source in the prior art
Reason, the order degree that nitrogen-doping enters the lattice of carbon material is limited, to also limit the conduction of carbon coating positive electrode
Performance and chemical property.The carbon material of this situ Nitrogen Doping provided by the invention has lead more superior than general carbon material
Electrical property can preferably promote the chemical property of material.
The present invention prepares the carbon-coated NCA positive electrodes of N doping using nitrogenous organic carbon source, used nitrogenous
The nitrogen-doped carbon that organic carbon source high-temperature process is formed can be uniformly coated on NCA ternary materials surface, can well reduce just
Contact of the pole material with electrolyte.
Due to the use of carbon source be nitrogenous organic carbon source, nitrogen source especially need not be added, uniform nitrogen can be synthesized
The carbon material of the carbon of doping, N doping has electronic conductivity more superior than general carbon material, can substantially improve cyclicity
Energy.
Preparation method provided by the invention need not mix organic carbon source and positive electrode, technique using any solvent
Simply, easy to operate.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Obtain other attached drawings according to these attached drawings.
Fig. 1 is the SEM figures of S4 samples made from the embodiment of the present invention 4；
Fig. 2 is the 1C discharge cycles curve graphs of the embodiment of the present invention 1 and reference examples 1；
Fig. 3 is the 1C discharge cycles curve graphs of the embodiment of the present invention 2 and reference examples 2；
Fig. 4 is the 1C discharge cycles curve graphs of the embodiment of the present invention 3 and reference examples 3；
Fig. 5 is the embodiment of the present invention 4 and reference examples 4, the 1C discharge cycles curve graphs of reference examples 5.
Specific implementation mode
In order to preferably illustrate the content of the invention, below by specific embodiment to further verification of the invention.It is special
Illustrate herein, embodiment is only the more directly description present invention, they are the part of the present invention, cannot be to structure of the present invention
At any restrictions.
Embodiment 1
The present invention also provides the preparation methods of the carbon-coated NCA positive electrodes of above-mentioned N doping, specifically include following steps：
S1, presoma is prepared：Using the sulfate of Ni, Co, Al as raw material, according to target product Ni0.8Co0.15Al0.05(OH)2
The amount ratio of the substance of each element, i.e. n in (y=0.15, z=0.05,1-y-z=0.8)Ni:nCo:nAl=80:15:5, it is accurate to claim
It takes and is configured to 1molL-1Sulfuric acid mixed salt solution, with 2molL-1NaOH be precipitating reagent, 1molL-1NH3·H2O
For complexing agent, by sodium hydroxide and NH3·H2O carries out being mixed to get lye, before reaction starts, first carries out bottom liquid deionized water
Stirring, mixed salt solution is added dropwise in the liquid of bottom, while lye is added, and the flow velocity of lye is regulated and controled with the variation of pH,
Salting liquid and lye form precipitation in beaker, and precipitation is washed, is dried to obtain presoma Ni0.8Co0.15Al0.05(OH)2。
S2, Li is prepared1.08Ni0.8Co0.15Al0.05O2Positive electrode matrix：By presoma Ni0.8Co0.15Al0.05(OH)2With
LiOH·H2O is 1 according to molar ratio:1.08, weigh the presoma Ni of corresponding amount0.8Co0.15Al0.05(OH)2、LiOH·H2O is mixed
After closing uniformly, 30h is sintered at 850 DEG C in oxygen atmosphere；Li is obtained after cooling, crushing, sieving1.08Ni0.8Co0.15Al0.05O2
Positive electrode matrix；
S3, washing：By Li1.08Ni0.8Co0.15Al0.05O2Positive electrode matrix carries out washing and reduces residual alkali, and ratio of water to material is
0.3:1, it filters, drying；
S4, the carbon-coated Li of N doping is prepared1.08Ni0.8Co0.15Al0.05O2Positive electrode：After washing
Li1.08Ni0.8Co0.15Al0.05O2The mass ratio of positive electrode matrix and pantothenic acid is 100:2, matrix, the pantothenic acid of corresponding amount are weighed,
After mixing, mixture is sintered 2h in argon gas atmosphere at 600 DEG C；It is obtained after cooling, sieving
Li1.08Ni0.8Co0.15Al0.05O2/ NC is denoted as sample S1.
Embodiment 2
The preparation method of the carbon-coated NCA positive electrodes of N doping provided in this embodiment, specifically includes following steps：
S1, presoma is prepared：Using the sulfate of Ni, Co, Al as raw material, according to target product Ni0.82Co0.15Al0.03
(OH)2The amount ratio of the substance of each element, i.e. n in (y=0.15, z=0.03,1-y-z=0.82)Ni:nCo:nAl=82:15:3,
Accurately weighs and be configured to 3molL-1Sulfuric acid mixed salt solution, with 6molL-1NaOH be precipitating reagent, 3molL- 1NH3·H2O is complexing agent, by sodium hydroxide and NH3·H2O be mixed to get lye, before reaction starts, first by bottom liquid go from
Sub- water is stirred, and mixed salt solution is added dropwise in the liquid of bottom, while lye is added, the flow velocity of lye with the variation of pH and into
Row regulation and control, salting liquid and lye form precipitation in beaker, and precipitation is washed, is dried to obtain presoma Ni0.82Co0.15Al0.03
(OH)2。
S2, Li is prepared1.06Ni0.82Co0.15Al0.03O2Positive electrode matrix：By presoma Ni0.82Co0.15Al0.03(OH)2With
LiOH·H2O is 1 according to molar ratio:1.06, weigh the presoma Ni of corresponding amount0.82Co0.15Al0.03(OH)2、LiOH·H2O is mixed
After closing uniformly, mixture is sintered 28h in oxygen atmosphere at 800 DEG C；It is obtained after cooling, crushing, sieving
Li1.06Ni0.82Co0.15Al0.03O2Positive electrode matrix；
S3, washing：By Li1.06Ni0.82Co0.15Al0.03O2Positive electrode matrix carries out washing and reduces residual alkali, ratio of water to material 1:
1, it filters, drying；
S4, the carbon-coated Li of N doping is prepared1.06Ni0.82Co0.15Al0.03O2Positive electrode：After washing
Li1.06Ni0.82Co0.15Al0.03O2The mass ratio of positive electrode matrix and PVP are 100:4, matrix, the PVP of corresponding amount are weighed, is mixed
After closing uniformly, mixture is sintered 3h in argon gas atmosphere at 700 DEG C；Li is obtained after cooling, sieving1.06Ni0.82Co0.15Al0.03O2/
NC is denoted as sample S2.
Embodiment 3
The preparation method of the carbon-coated NCA positive electrodes of N doping provided in this embodiment, specifically includes following steps：
S1, presoma is prepared：Using the sulfate of Ni, Co, Al as raw material, according to target product Ni0.88Co0.1Al0.02(OH)2
The amount ratio of the substance of each element, i.e. n in (y=0.1, z=0.02,1-y-z=0.88)Ni:nCo:nAl=88:10:2, it is accurate to claim
It takes and is configured to 2molL-1Sulfuric acid mixed salt solution, with 4molL-1NaOH be precipitating reagent, 2molL-1NH3·H2O
For complexing agent, by sodium hydroxide and NH3·H2O carries out being mixed to get lye, before reaction starts, first carries out bottom liquid deionized water
Stirring, mixed salt solution is added dropwise in the liquid of bottom, while lye is added, and the flow velocity of lye is regulated and controled with the variation of pH,
Salting liquid and lye form precipitation in beaker, and precipitation is washed, is dried to obtain presoma Ni0.88Co0.1Al0.02(OH)2。
S2, Li is prepared1.04Ni0.88Co0.1Al0.02O2Positive electrode matrix：By presoma Ni0.88Co0.1Al0.02(OH)2With
LiOH·H2O is 1 according to molar ratio:1.04, weigh the presoma Ni of corresponding amount0.88Co0.1Al0.02(OH)2、LiOH·H2O is mixed
After closing uniformly, mixture is sintered for 24 hours in oxygen atmosphere at 750 DEG C；It is obtained after cooling, crushing, sieving
Li1.04Ni0.88Co0.1Al0.02O2Positive electrode matrix；
S3, washing：By Li1.04Ni0.88Co0.1Al0.02O2Positive electrode matrix carries out washing and reduces residual alkali, ratio of water to material 2:
1, it filters, drying；
S4, the carbon-coated Li of N doping is prepared1.04Ni0.88Co0.1Al0.02O2Positive electrode：After washing
Li1.04Ni0.88Co0.1Al0.02O2The mass ratio of positive electrode matrix and PAN are 100:6, matrix, the PAN of corresponding amount are weighed, is mixed
After closing uniformly, mixture is sintered 4h in nitrogen atmosphere at 800 DEG C；Li is obtained after cooling, sieving1.04Ni0.88Co0.1Al0.02O2/
NC is denoted as sample S3.
Embodiment 4
The preparation method of the carbon-coated NCA positive electrodes of N doping provided in this embodiment, specifically includes following steps：
S1, presoma is prepared：Using the sulfate of Ni, Co, Al as raw material, according to target product Ni0.92Co0.06Al0.02
(OH)2The amount ratio of the substance of each element, i.e. n in (y=0.06, z=0.02,1-y-z=0.92)Ni:nCo:nAl=92:6:2, it is accurate
Really weighs and be configured to 1molL-1Sulfuric acid mixed salt solution, with 3molL-1NaOH be precipitating reagent, 1molL- 1NH3·H2O is complexing agent, by sodium hydroxide and NH3·H2O be mixed to get lye, before reaction starts, first by bottom liquid go from
Sub- water is stirred, and mixed salt solution is added dropwise in the liquid of bottom, while lye is added, the flow velocity of lye with the variation of pH and into
Row regulation and control, salting liquid and lye form precipitation in beaker, and precipitation is washed, is dried to obtain presoma Ni0.92Co0.06Al0.02
(OH)2。
S2, Li is prepared1.02Ni0.92Co0.06Al0.02O2Positive electrode matrix：By presoma Ni0.92Co0.06Al0.02(OH)2With
LiOH·H2O is 1 according to molar ratio:1.02, weigh the presoma Ni of corresponding amount0.92Co0.06Al0.02(OH)2、LiOH·H2O is mixed
After closing uniformly, mixture obtains after being sintered 20h cooling, crushing, sieving at 700 DEG C in oxygen atmosphere
Li1.02Ni0.92Co0.06Al0.02O2Positive electrode matrix；
S3, washing：By Li1.02Ni0.92Co0.06Al0.02O2Positive electrode matrix carries out washing and reduces residual alkali, ratio of water to material 5:
1, it filters, drying；
S4, the carbon-coated Li of N doping is prepared1.02Ni0.92Co0.06Al0.02O2Positive electrode：After washing
Li1.02Ni0.92Co0.06Al0.02O2The mass ratio of positive electrode matrix and EDTA are 100:8, matrix, the EDTA of corresponding amount are weighed,
After mixing, mixture is sintered 2h in nitrogen atmosphere at 600 DEG C；It is obtained after cooling, sieving
Li1.02Ni0.92Co0.06Al0.02O2/ NC is denoted as sample S4.
Comparative example 1
Difference lies in be directly added without organic carbon source, dinectly bruning obtains to this comparative example in step s 4 with embodiment 1
The carbon-coated NCA control samples of N doping are not carried out, D1 is denoted as.
Comparative example 2
This comparative example the difference from example 2 is that, be directly added without organic carbon source in step s 4, dinectly bruning obtains
The carbon-coated NCA control samples of N doping are not carried out, D2 is denoted as.
Comparative example 3
Difference lies in be directly added without organic carbon source, dinectly bruning obtains to this comparative example in step s 4 with embodiment 3
The carbon-coated NCA control samples of N doping are not carried out, D3 is denoted as.
Comparative example 4
Difference lies in be directly added without organic carbon source, dinectly bruning obtains to this comparative example in step s 4 with embodiment 4
The carbon-coated NCA control samples of N doping are not carried out, D4 is denoted as.
Comparative example 5
Difference lies in be added glucose and replace EDTA, calcining is not had this comparative example in step s 4 with embodiment 4
The common carbon-coated NCA control samples of N doping, are denoted as D5.
Above-mentioned NCA positive electrodes sample S1~S4, D1~D5 are analyzed as follows：
1) Electron micrographs are carried out to sample S4, result is as shown in Fig. 1, from figure 1 it will be seen that nitrogen-doped carbon is equal
It is coated on the surface of NCA positive electrode matrixes evenly；
2) electric discharge is carried out after above-mentioned NCA positive electrodes sample S1~S4, D1~D5 being assembled into CR2025 button cells
It can test, the method that CR2025 button cells are made is as follows：
A1, pyrrolidone is given a tongue-lashing using N- methyl as solvent, by the difference of above-described embodiment 1~4 LiNi obtained0.8Co0.15Al0.05O2
Positive electrode sample S1~S4, D1~D5 are 8 according to the amount ratio of substance with Kynoar and conductive black:1:1 weigh after plus
Enter N- methyl to give a tongue-lashing in pyrrolidone, carrying out magnetic agitation makes it be uniformly mixed, and obtains mixed slurry；
A2, then, the mixed slurry that step A1 has been configured uniformly are coated on aluminium foil, and dry 12h is obtained at 80 DEG C
To positive plate, the round positive plate of a diameter of 11mm is then made with card punch；Round positive plate is weighed to calculate anode
Then round positive plate is compacted with the power of 40MPa to get anode by the quality of material on tablet press machine；
A3, in vacuum glove box, with anode made from step A2, using lithium metal as cathode, Celgard2400 is more
Hole polyethylene film is diaphragm, with LiPF6/EC (ethylene carbonate)+DMC (dimethyl carbonate)+EMC (methyls of 1mol/L
Ethyl ester) (EC：DMC：The volume ratio of EMC is 1:1:1) it is electrolyte；According to positive shell-anode-diaphragm-electrolyte-
The sequence of cathode lithium piece-anode coat is assembled, and CR2025 button cells are obtained, and is denoted as number DC1~DC9 respectively.
And to numbering the battery sample for being DC1~DC9 at 25 DEG C, 3.0~4.3V of voltage range, 0.1C, 0.5C, 1C are carried out
Discharge performance is tested, shown in the following Tables 1 and 2 of performance test：
The 1C discharge performances of 1 battery sample DC1~DC9 of table and recycle 100 capacity retention ratios
Discharge performance test results of the 2 battery sample DC1~DC9 of table in 0.1C, 0.5C, 1C
From upper table 1, table 2 as a result, can be learnt in conjunction with attached drawing 2~5：The carbon-coated NCA anodes material of N doping of the present invention
Material (DC1~DC4) cycle performance to be far superior to its it is corresponding do not carry out coated modified carbon NCA positive electrodes (DC5~
DC8 the NCA positive electrodes (DC9) of common carbon material coating modification are carried out) and.In addition, from the point of view of the data in table 1, commonly
The capacity retention ratio of the NCA positive electrodes (DC9) of carbon material coating modification is higher than the NCA anode materials for not carrying out coated modified carbon
Expect (DC8), illustrates that coated modified carbon can largely improve the discharge capacitance of ion battery, improve its cyclicity
Energy.
The above is specific implementation mode of the invention, but any restrictions cannot be constituted to the present invention, therefore is needed special
It points out, it is every based on the present invention, it is made any modification and is all fallen within the scope of the present invention with improvement.
Claims (9)
1. a kind of carbon-coated NCA positive electrodes of N doping, which is characterized in that its general structure is LixNi1-y-zCoyAlzO2/
NC, 1≤x≤1.08,0.05 ＜ y≤0.15,0 ＜ z≤0.05, NC is nitrogen-doped carbon organic matter；
LixNi1-y-zCoyAlzO2Positive electrode matrix：The mass ratio of NC is 100:(2~8).
2. the carbon-coated NCA positive electrodes of a kind of N doping according to claim 1, which is characterized in that above-mentioned NC be containing
The Organic Compounds high-temperature calcination of nitrogen is formed, and the nitrogenous Organic Compounds are specially ethylenediamine tetra-acetic acid, polyethylene
The combination of one or more of pyrrolidones, polyacrylonitrile or pantothenic acid.
3. a kind of lithium ion battery, the lithium ion battery include：Anode, cathode, diaphragm and electrolyte, which is characterized in that structure
It is the carbon-coated NCA positive electrodes of N doping as claimed in claim 1 or 2 at the positive electrode in the anode.
4. a kind of preparation method of the carbon-coated NCA positive electrodes of N doping, which is characterized in that specifically include following steps：
S1, presoma is prepared：Prepare NCA ternary material precursors Ni1-y-zCoyAlz(OH)2, 0.05 ＜ y≤0.15,0 ＜ z≤
0.05；
S2, NCA positive electrode matrixes are prepared：By presoma Ni1-y-zCoyAlz(OH)2With LiOHH2O is 1 according to molar ratio:(1
~1.08) presoma, the LiOHH of corresponding amount, are weighed2O is calcined, calcination temperature under oxidizing atmosphere after mixing
700~850 DEG C, 20~30h of calcination time；NCA positive electrode matrixes are obtained after cooling, crushing, sieving；
S3, washing：NCA positive electrodes matrix is subjected to washing and reduces residual alkali, the mass ratio of water and NCA matrixes is (0.3~5):
1, it filters, drying；
S4, the carbon-coated NCA positive electrodes of N doping are prepared：By after step S3 washing NCA positive electrodes matrix with it is nitrogenous
The mass ratio of Organic Compounds is 100:(2~8) weigh the matrix of corresponding amount, nitrogenous Organic Compounds, are uniformly mixed
Afterwards, it is calcined under an inert atmosphere, 600~800 DEG C, 2~4h of calcination time of calcination temperature, it is nitrogenous in high-temperature burning process
Organic Compounds formed NC be uniformly coated on NCA ternary materials surface to get general structure be LixNi1-y- zCoyAlzO2The carbon-coated NCA positive electrodes of N doping of/NC, wherein：1≤x≤1.08,0.05 ＜ y≤0.15,0 ＜ z≤
0.05。
5. a kind of preparation method of the carbon-coated NCA positive electrodes of N doping according to claim 4, which is characterized in that
Presoma Ni in step S11-y-zCoyAlz(OH)2Prepare it is specific as follows：
Using the sulfate of Ni, Co, Al or nitrate as raw material, according to the amount ratio of the substance of each element in target product, i.e. nNi:
nCo:nAl=(1-y-z):y:Z is accurately weighed and and is configured to 1~3molL-1Sulfate/nitrate mixed solution, with 2
~6molL-1NaOH be precipitating reagent, 1~3molL-1NH3·H2O is complexing agent, by sodium hydroxide and NH3·H2O is carried out
Lye is mixed to get first to be stirred deionized water as bottom liquid before reaction starts, mixed salt solution is then added dropwise to bottom
In liquid, while lye is added, the flow velocity of lye is regulated and controled with the variation of pH, and salting liquid and lye are formed in beaker and sunk
It forms sediment, precipitation is washed, is dried to obtain presoma Ni1-y-zCoyAlz(OH)2。
6. a kind of preparation method of the carbon-coated NCA positive electrodes of N doping according to claim 4 or 5, feature exist
In,
In step S4, above-mentioned NC is that nitrogenous Organic Compounds high-temperature calcination is formed, the nitrogenous Organic Compounds tool
Body is ethylenediamine tetra-acetic acid, polyvinylpyrrolidone, the combination of one or more of polyacrylonitrile or pantothenic acid.
7. a kind of preparation method of the carbon-coated NCA positive electrodes of N doping according to claim 4 or 5, feature exist
In,
In step S4, inert atmosphere is nitrogen atmosphere or argon gas atmosphere.
8. a kind of preparation method of the carbon-coated NCA positive electrodes of N doping according to claim 4 or 5, feature exist
In,
The method further includes step S5：Positive plate is made in the carbon-coated NCA positive electrodes of N doping made from step S4, with
Negative plate, diaphragm, electrolyte together, according to the sequence of positive shell-positive plate-diaphragm-electrolyte-negative plate-anode coat
It carries out assembling obtained lithium ion battery.
9. a kind of preparation method of the carbon-coated NCA positive electrodes of N doping according to claim 8, which is characterized in that
Step S5 includes the following steps：
S51, pyrrolidone is given a tongue-lashing using N- methyl as solvent, nitrogen-doped carbon cladding NCA positive electrodes and polyvinylidene fluoride is made in step S4
Alkene and conductive black are 8 according to the amount ratio of substance:1:1 weigh after be added there is N- methyl to give a tongue-lashing in the small reagent bottle of pyrrolidone, carry out
Magnetic agitation makes it be uniformly mixed, and obtains mixed slurry；
S52, then, by mixed slurry configure uniformly coated on aluminium foil, then dries 10~14h at 70~90 DEG C
Positive plate is obtained, then punches and a diameter of 11mm positive plates is made, positive plate is weighed to calculate the quality of positive electrode, with
Positive plate is compacted on tablet press machine with the power of 35~45MPa afterwards；
S53, in vacuum glove box, the positive plate after the compacting prepared with step S52 is anode, and lithium metal is cathode,
The porous polyethylene films of Celgard2400 are diaphragm, using the LiPF6/EC+DMC+EMC of 1mol/L as electrolyte, wherein EC：DMC：
The volume ratio of EMC is 1:1:1；It is carried out according to the sequence of positive shell-positive plate-diaphragm-electrolyte-negative plate-anode coat
Assembling, obtains CR2025 button cells.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110783564A (en) * | 2019-11-07 | 2020-02-11 | 珠海冠宇电池有限公司 | Nitrogen-doped carbon-coated ternary positive electrode material and preparation method thereof |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509784A (en) * | 2011-10-17 | 2012-06-20 | 北大先行科技产业有限公司 | Preparation method of lithium ion battery ternary cathode material |
| CN103073062A (en) * | 2011-10-26 | 2013-05-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of manganese-series positive electrode material used in lithium ion secondary battery |
| CN104129781A (en) * | 2014-07-25 | 2014-11-05 | 深圳新宙邦科技股份有限公司 | In-situ nitrogen-doped porous graphene and preparation method thereof |
| CN104466154A (en) * | 2014-12-10 | 2015-03-25 | 哈尔滨工业大学（威海） | Preparation method of lithium ion battery positive material nickel cobalt aluminum |
| CN106981642A (en) * | 2017-05-22 | 2017-07-25 | 中南大学 | A kind of spherical vanadium phosphate manganese sodium composite of nitrating carbon coating and preparation method thereof and the application in sodium-ion battery |
| CN107579237A (en) * | 2017-09-13 | 2018-01-12 | 桑顿新能源科技有限公司 | A kind of tertiary cathode material preparation method and tertiary cathode material |
| CN107611411A (en) * | 2017-10-10 | 2018-01-19 | 中国科学院新疆理化技术研究所 | A kind of preparation method and application of the classifying porous nitrogen-doped carbon bag silicon composite of three-dimensional |
| CN108242540A (en) * | 2018-01-04 | 2018-07-03 | 中南大学 | A kind of carbon coating vanadium phosphate sodium microballoon and preparation method thereof and the application as sodium-ion battery positive material |
-
2018
- 2018-07-27 CN CN201810845384.5A patent/CN108666559A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509784A (en) * | 2011-10-17 | 2012-06-20 | 北大先行科技产业有限公司 | Preparation method of lithium ion battery ternary cathode material |
| CN103073062A (en) * | 2011-10-26 | 2013-05-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of manganese-series positive electrode material used in lithium ion secondary battery |
| CN104129781A (en) * | 2014-07-25 | 2014-11-05 | 深圳新宙邦科技股份有限公司 | In-situ nitrogen-doped porous graphene and preparation method thereof |
| CN104466154A (en) * | 2014-12-10 | 2015-03-25 | 哈尔滨工业大学（威海） | Preparation method of lithium ion battery positive material nickel cobalt aluminum |
| CN106981642A (en) * | 2017-05-22 | 2017-07-25 | 中南大学 | A kind of spherical vanadium phosphate manganese sodium composite of nitrating carbon coating and preparation method thereof and the application in sodium-ion battery |
| CN107579237A (en) * | 2017-09-13 | 2018-01-12 | 桑顿新能源科技有限公司 | A kind of tertiary cathode material preparation method and tertiary cathode material |
| CN107611411A (en) * | 2017-10-10 | 2018-01-19 | 中国科学院新疆理化技术研究所 | A kind of preparation method and application of the classifying porous nitrogen-doped carbon bag silicon composite of three-dimensional |
| CN108242540A (en) * | 2018-01-04 | 2018-07-03 | 中南大学 | A kind of carbon coating vanadium phosphate sodium microballoon and preparation method thereof and the application as sodium-ion battery positive material |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110783564A (en) * | 2019-11-07 | 2020-02-11 | 珠海冠宇电池有限公司 | Nitrogen-doped carbon-coated ternary positive electrode material and preparation method thereof |
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| CN114039048B (en) * | 2020-08-18 | 2024-01-30 | 吉林吉恩镍业股份有限公司 | Preparation method of semi-doped and semi-coated NCA positive electrode material |
| CN113735195A (en) * | 2021-08-31 | 2021-12-03 | 蜂巢能源科技有限公司 | Method for coating layered positive electrode material of lithium battery and carbon-doped calcium-coated layered positive electrode material |
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| WO2023093190A1 (en) * | 2021-11-26 | 2023-06-01 | 广东邦普循环科技有限公司 | Nitrogen-doped-polymeric porous nanopowder-deposited positive electrode material, preparation method therefor, and application thereof |
| GB2619189A (en) * | 2021-11-26 | 2023-11-29 | Guangdong Brunp Recycling Technology Co Ltd | Nitrogen-doped-polymeric porous nanopowder-deposited positive electrode material, preparation method therefor, and application thereof |
| GB2619189B (en) * | 2021-11-26 | 2024-06-05 | Guangdong Brunp Recycling Technology Co Ltd | Nitrogen-doped-polymeric porous nanopowder-deposited positive electrode material, preparation method therefor, and application thereof |
| CN114744196A (en) * | 2022-03-28 | 2022-07-12 | 蜂巢能源科技股份有限公司 | C-doped and coated cobalt-free cathode material, preparation method and lithium ion battery |
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