CN109888197A - A kind of high magnification long circulating performance multi-element composite positive pole material and preparation method thereof - Google Patents
A kind of high magnification long circulating performance multi-element composite positive pole material and preparation method thereof Download PDFInfo
- Publication number
- CN109888197A CN109888197A CN201811598179.XA CN201811598179A CN109888197A CN 109888197 A CN109888197 A CN 109888197A CN 201811598179 A CN201811598179 A CN 201811598179A CN 109888197 A CN109888197 A CN 109888197A
- Authority
- CN
- China
- Prior art keywords
- compound
- aluminium
- positive pole
- preparation
- composite positive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of high magnification long circulating performance multi-element composite positive pole material and preparation method thereof, the positive electrode is hollow structure ball of the D50 at 2~7 microns, chemical formula LixNiyCozMn1‑y‑zO2；Doped with the Z compound of mass ratio 0.02%~1% inside it, Z is at least one of Nb or Ta；Its surface, which is coated with, accounts for aluminium compound of the substrate quality than 0.01%~1%；In the chemical formula, x, y, z is the value of the molar ratio of coherent element, respectively 0.9 < x < 1.3,0.2≤y < 1,0 < z < 0.5, y+z≤1.Hollow structure of the present invention can enhance infiltration and liquid-keeping property to nonaqueous electrolyte, can effectively shorten the path of lithium ion transport, provide resulting structure support for high current high power charging-discharging；The hardness that the present invention both can increase hollow ball structure can also stablize lattice knot, while play biggish improvement to the cycle performance of material.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical fields, and in particular to a kind of high magnification long circulating performance is polynary
Composite positive pole and preparation method thereof.
Background technique
Lithium ion battery because its specific capacity is high, have extended cycle life, have a safety feature, is environmentally friendly the advantages that at home and abroad
It is used widely in mobile terminal devices such as various mobile phones, notebooks.Wantonly due to increasing environmental pollution in recent years, haze sky
Cruel, national and local governments are extremely urgent to reduction vehicle emission pollution and improvement ambient air quality, and the micro- mixing system of 48V is answered
It transports and gives birth to, and its required lithium battery is also at urgent development status, and has significant market.
The exploitation difficult point of the micro- mixing system of 48V is: 1) wide to use temperature (- 45 DEG C~75 DEG C)；2) long life (10
Year)；3) high rate capability (20C~30C)；Optimising and adjustment can be carried out by the heat management system of battery pack using temperature,
And the performance in terms of other two relies primarily on the optimization of battery material then to reach.Conventional lithium battery material is extremely difficult to above
Two kinds of requirements, or be difficult to take into account high rate performance and cycle performance.
Currently used micro- mixed cell positive material mainly has the NCM111 material of LFP material and small particle, but LFP voltage
Platform low energy densities are low, and also very complete difficulty meets above-mentioned high power discharge demand to the NCM111 material of small particle.Mesh in a word
It is preceding to be badly in need of a positive electrode that can satisfy harsh high rate charge-discharge performance and long circulating performance of exploitation.
In order to meet requirement of the micro- mixing system of 48V to multiplying power and circulation, it is more a kind of high magnification long circulating performance has been provided
First composite positive pole and preparation method thereof；Infiltration and liquid-keeping property to nonaqueous electrolyte can be enhanced in hollow structure, can be with
It effectively shortens the path of lithium ion transport, provides effective structural support for high current high power charging-discharging；On the other hand, in
Although hollow structure can be improved high rate performance, but hollow structure is easily broken during roll-in and hollow structure and electrolysis
Liquid contact easily causes more side reaction excessively to cause cycle performance to be deteriorated, so the present invention is proposed using with hard special
Property niobium or tantalum doping can both increase the hardness of hollow spherical structure and can also stablize lattice knot, while it is further to carry out surface cladding
Inhibit the side reaction between electrolyte, biggish improvement is played to the cycle performance of material.
Summary of the invention
In order to meet requirement of the micro- mixing system of 48V to multiplying power and circulation, the object of the present invention is to provide a kind of high magnifications
Performance and the multi-element composite positive pole material of long circulating performance and preparation method thereof；Hollow structure can be enhanced to nonaqueous electrolyte
Infiltration and liquid-keeping property, can effectively shorten the path of lithium ion transport, provide effectively for high current high power charging-discharging
Structural support；On the other hand, although high rate performance can be improved in hollow structure, but hollow structure is easy during roll-in
Broken and hollow structure easily causes more side reaction excessively with electrolyte contacts to cause cycle performance to be deteriorated, so this
Invention proposes that the hardness that can have both increased hollow spherical structure using niobium or the tantalum doping with hardware features can also stablize lattice knot, together
The surface Shi Jinhang cladding further suppresses the side reaction between electrolyte, plays biggish improvement to the cycle performance of material.
In order to achieve the above object, the present invention has following technical scheme:
A kind of high magnification long circulating performance multi-element composite positive pole material of the invention, the positive electrode are D50 2~7
The hollow structure ball of micron, chemical formula LixNiyCozMn1-y-zO2；Doped with the Z chemical combination of mass ratio 0.02%~1% inside it
Object, Z are at least one of Nb or Ta；Its surface, which is coated with, accounts for aluminium compound of the substrate quality than 0.01%~1%；Describedization
In formula, x, y, z is the value of the molar ratio of coherent element, respectively 0.9 < x < 1.3,0.2≤y < 1,0 < z < 0.5, y+z≤1.
A kind of preparation method of high magnification long circulating performance multi-element composite positive pole material of the invention, comprising the following steps:
(1) carbon core-C core NiyCozMn1-y-z(OH)2The preparation of presoma:
Compound concentration is the finely dispersed carbon ball liquid solution of 0.01wt%~0.5wt%, and wherein the D50 of carbon ball body is
0.01~1 μm, soluble nickel source compound, cobalt source compound and manganese source compound are then pressed into Ni:Co:Mn=y:z:(1-y-
Z) molar ratio is made into mixed solution A, and the concentration of mixed solution A is 1~3mol/L；Configuration concentration is the NaOH of 4~10mol/L
Solution B；Compound concentration is the ammonia spirit C of 4~10mol/L as complexing agent；Tri- kinds of solution metering pumps of A, B, C are connected respectively
Continuous to be added in the reaction vessel with stirring, reaction temperature is maintained at 30~70 DEG C, and pH is maintained at 9~12, mixing speed 200-
The whole process of 800r/min, reaction lead to inert gas shielding；Obtained precipitating is filtered, washed after reaction, in 90-
Dry 4-12h at 180 DEG C；
(2) hollow structure mixes the Li of ZxNiyCozMn1-y-zO2The preparation of basis material:
C core Ni will be obtained in lithium salts and step (1)yCozMn1-y-z(OH)2In molar ratio Li/M be equal to 1.05~1.2 and with
NiyCozMn1-y-z(OH)2The Z compound that mass ratio is 0.02%~1% carries out mixed at high speed, M NiyCozMn1-y-z(OH)2In
Total metal molar number, Z be at least one of Nb or Ta；Uniformly mixed material is sintered in high temperature furnace, atmosphere be containing
Oxygen atmosphere, high temperature furnace are warming up to 300~750 DEG C with the heating rate of 1~5 DEG C/min, keep the temperature 1~6h, then with the heating rate
750~960 DEG C are warming up to, 6~18h is kept the temperature；Material furnace cooling, screening, removes iron at broken, crushing, obtains hollow structure and mixes niobium
LixNiyCozMn1-y-zO2Basis material；
(3) the hollow Li for mixing Z of Al is coatedxNiyCozMn1-y-zO2The preparation of multi-element composite positive pole material；
1. dry method coats aluminium compound；Matrix Li obtained by step (2)xNiyCozMn1-y-zO2With the matter calculated by aluminium content
Amount mixes 3~60min in high speed mixer high speed than 0.01%~1% nanoscale aluminium compound, keeps aluminium compound uniform
Be coated on matrix, in the hollow Li for mixing Z that 400-800 DEG C of 4~12h of constant temperature is evenly coatedxNiyCozMn1-y- zO2Multi-element composite positive pole material, Z are at least one of Nb or Ta；
2. wet process coats aluminium compound；Matrix Li obtained by step (2)xNiyCozMn1-y-zO2It is dispersed in water, keeps it solid
Content is 10%~80%；Aluminium content is added and is calculated as the aluminium compound of mass ratio 0.01%~1%, quickly stir 0.2h~
4h sufficiently reacts；The slurry stirred evenly is added in double helix vacuum dryer or Rotary Evaporators and is dried in vacuo；?
400-800 DEG C of 4~12h of constant temperature and the hollow Li for mixing Z being evenly coatedxNiyCozMn1-y-zO2Multi-element composite positive pole material, Z
For at least one of Nb or Ta.
Wherein, core balls used in preparation process be carbosphere, ball-type graphite, carbon ball, fullerene it is one such or
It is a variety of.
Wherein, core mean diameter of a ball D50 used in preparation process is 0.01~1 micron；The C core
NiyCozMn1-y-z(OH)2The average diameter D50 of presoma is at 2~7 microns；The Li/M molar ratio is that 1.05~1.2, M is
NiyCozMn1-y-z(OH)2The middle metalliferous total metal molar number of institute.
Wherein, the nickel source compound is one of nickel sulfate, nickel chloride, nickel nitrate, nickel acetate, chloric acid nickel or more
Kind；Cobalt source compound is one of cobaltous sulfate, cobalt chloride, cobalt nitrate, cobaltous chlorate or a variety of；Manganese source compound be manganese sulfate,
One of manganese chloride, manganese nitrate, manganous bromide are a variety of；The lithium salts, using in lithium carbonate, monohydrate lithium hydroxide, lithium nitrate
It is one or more.
Wherein, the Z compound is adulterated, Z is at least one of Nb or Ta, and the niobium compound of use there are five oxidations two
It is niobium, columbium dioxide, columbium sesquioxide, columbium dioxide, columbium pentachloride, one or more in niobium (Nb) pentafluoride, and be not limited to above-mentioned
Contain niobium compound；The tantalum compound of use has tantalum pentoxide, tantalum dioxide, three two tantalums of oxidation, tantalum dioxide, phosphoric
It is one or more in tantalum, tantalum pentafluoride, and it is not limited to above-mentioned containing niobium compound, doping is in 0.02~1wt%, by Z's
Content calculates；The hollow structure for being evenly coated Al mixes the Li of ZxNiyCozMn1-y-zO2Multi-element composite positive pole material average grain diameter
At 2~7 microns, Z is at least one of Nb or Ta.
Wherein, 1. dry method cladding described in aluminium compound, using in aluminium oxide, aluminium hydroxide, aluminum phosphate, aluminum fluoride one
Kind is a variety of, and covering amount is in 0.01~1wt%, by Mass Calculation contained by wherein aluminium；2. aluminium compound described in wet process cladding,
It is one of or more using aluminium isopropoxide, aluminum oxyhydroxide, aluminum nitrate, aluminium chloride, alumina fluid dispersion, aluminum phosphate dispersion liquid
Kind, the covering amount of aluminium is in 0.01~1wt%, by Mass Calculation contained by wherein aluminium.
Wherein, in step (3) 1. in coating equipment used be high speed mixer, the cladding time is 3~60min, is coated
Speed is 500~2000r/min, and temperature of plate is 10~80 DEG C.
Wherein, step (3) 2. in the solid content of material and solvent be 10~80%, 10 DEG C~70 DEG C of feed liquid temperature, when
Between 10min~4h, 100~1000r/min of mixing speed.
Wherein, the purpose of the 2. middle double helix vacuum drying or Rotary Evaporators drying in step (3) is to accelerate to do
Dry speed and guarantee that aluminium keeps good being evenly coated property in the process of drying, is also avoided that Li in material+Loss, influence
The chemical property of material.
Beneficial effect
Gained multi-element composite material has hollow spherical structure, and large specific surface area can enhance connecing for positive electrode and electrolyte
Touching, helps the abundant infiltration with electrolyte, and the distance of the lithium ion that effectively shortens insertion and abjection mentions for battery high current charge-discharge
For structure basis, to promote the high rate performance of battery.But hollow spherical structure is easily broken in nipping process, while in
Hollow structure easily causes more side reaction excessively with electrolyte contacts to cause cycle performance to be deteriorated, so hard using having
Niobium or the tantalum doping of characteristic, which can both increase the hardness of hollow spherical structure, can also stablize lattice structure, at the same carry out surface coat into
One step inhibits the side reaction between electrolyte, plays biggish improvement to the cycle performance of material.
Compared with prior art, technical solution of the present invention supports precursor construction using carbon ball, and the later period is allowed to by sintering
Formed hollow structure, compared to other organic solvents remove astrosphere method more economical and effective, the method cost is relatively low and
It is easily industrialized.
A kind of high magnification long circulating performance multi-element composite positive pole material of the invention, high rate performance 5C/0.2C >=90%；
5C recycles 500 weeks conservation rate >=90%.
Detailed description of the invention
Fig. 1 is the XRD spectrum of the LiNi0.6Co0.2Mn0.2O2 prepared in embodiment 1；
Fig. 2 is the different multiplying discharge capacitance figure of embodiment 1 and comparative example 1,2,3；
Fig. 3 is the 5C circulation conservation rate figure of embodiment 1 and comparative example 1,2,3；
Fig. 4 is the 1C circulation conservation rate figure of embodiment 1 and comparative example 1,2,3.
Specific embodiment
For a further understanding of the present invention, the present invention is made below in conjunction with specification and specific preferred embodiment further
Description, but protection scope not thereby limiting the invention.
Embodiment 1
Select D50 that reaction kettle high speed dispersion 20min is added for 0.5 micron of ball-type graphite, then by nickel sulfate, sulfuric acid
Cobalt and manganese sulfate are made into mixed solution and are uniformly mixed according to Ni:Co:Mn molar ratio for 0.6:0.2:0.2, tri- kinds of mistakes of Ni, Co, Mn
The total mole number for crossing metal ion is 2mol/L, then by the NaOH solution of 6mol/L and transition metal ion solution and 6mol/L
Ammonium hydroxide simultaneously be added in reaction vessel, control reaction system pH value be 11.5, reaction temperature be 60 DEG C.Then it will obtain
Precipitating be filtered, washed after, dry 10 hours at 110 DEG C, obtain C core Ni0.6Co0.2Mn0.2 (OH) 2 presoma.By hydrogen
Lithia and C core Ni0.6Co0.2Mn0.2 (OH) 2 according to Li/M=1.14 (M=Ni0.6Co0.2Mn0.2 (OH) 2) ratio
The Nb2O5 (being calculated with Nb with forerunner's body mass ratio) of additional 0.1wt% is mixed, and is uniformly mixed in high speed mixer, with 3
DEG C/min heating rate is warming up to 650 DEG C, keeps the temperature 2h, then heat to 850 DEG C of calcining 12h, atmosphere for 60L/min oxygen,
Material furnace cooling smashes it through 325 meshes except the Nb doping for the hollow structure for obtaining 4.5 microns after iron is 0.1%
LiNi0.6Co0.2Mn0.2O2 basis material.High speed mixing is added in 2000g basis material and 5.67g nanoscale Al2O3 to set
It is standby, 325 meshes are crossed after 3000r/min mixing 5min, 550 DEG C of sintering 5h, and it is equal to finally obtain the cladding that Al covering amount is 0.15%
The even hollow LiNi0.6Co0.2Mn0.2O2 composite material for mixing Nb, the XRD diagram of composite material are as shown in Figure 1.The result shows that institute
Obtaining LiNi0.6Co0.2Mn0.2O2 is pure phase, has preferable crystallinity.
By the hollow LiNi0.6Co0.2Mn0.2O2 composite positive pole of above-mentioned synthesis, acetylene black, KS-6, PVDF according to
The ratio that mass ratio is 9.0 ︰, 0.4 ︰, 0.3 ︰ 0.3 is uniformly mixed, and appropriate NMP is added, and uniform slurry is made in stirring；Slurry is equal
It is applied on aluminium foil evenly, after being put into air dry oven drying, places into 120 DEG C of vacuum oven and be dried in vacuo 12 hours；From
The disk that diameter is 16mm so is gone out with sheet-punching machine after cooling, disk is placed on after the pressure compaction for using 10MPa on tablet press machine i.e.
Obtain positive plate.It is anode with homemade positive plate, lithium piece is cathode, and Celgard2400 microporous polypropylene membrane is diaphragm,
The LiPF6/EC+DMC (v:v=1:1) of 1mol/L is electrolyte, is all full of argon 0.1ppm is below in water content and oxygen content
It is assembled into CR2016 type button cell in the glove box of gas, is filled in 2.75~4.25V voltage range with the multiplying power of 0.1C
Discharge test, discharge capacity reaches 178mAh/g to material for the first time, and it is 95% that button cell, which recycles 100 weeks capacity retention ratios,
Embodiment 2
Based on the hollow LiNi0.6Co0.2Mn0.2O2 basis material mixed Nb and be 0.1% made from embodiment 1, stirring
1000mL H2O is added in tank, after 30 DEG C of constant temperature 10min, it is nano oxidized that 56g is added in the material after the above-mentioned sieving of 2000g is added
Aluminium dispersion liquid, 30 DEG C of constant temperature stir 1h, after with Rotary Evaporators carry out vacuum drying, the material after drying is put into high temperature furnace
In, 325 meshes are crossed after 700 DEG C of sintering 10h, finally obtain Al covering amount be 0.15% be evenly coated hollow mix Nb's
LiNi0.6Co0.2Mn0.2O2 multi-element composite positive pole material, the other the same as in Example 1
Embodiment 3
In addition to replacing Nb2O5 with Ta2O5, the other the same as in Example 1, the tantalum doping for the hollow structure being evenly coated
LiNi0.6Co0.2Mn0.2O2 composite positive pole
Comparative example 1
The other the same as in Example 1 in addition to being added without ball-type graphite during precursor preparation
Comparative example 2
The other the same as in Example 1 in addition to being added without Nb2O5
Comparative example 3
Other are the same as embodiment 1 in addition to without cladding
In the embodiment of the present invention, Li source compound only lists lithium hydroxide, and monohydrate lithium hydroxide, lithium nitrate etc. are at this
Also the effect of lithium ion can be provided during invention, therefore monohydrate lithium hydroxide and lithium nitrate are all suitable for the present invention.Equally
Nickel source compound, manganese source compound and cobalt source compound can also be by being replaced except cited sulfate；NbO2,Nb2O3,
NbCl5 and NbF5 etc. is used as mixing the source Nb.TaO2, Ta2O3, TaCl5 and TaF5 etc. are used as mixing the source Ta embodiment
Only for illustrating the present invention, the scope and spirit that should not be understood to limit the present.
Embodiment 1 has good high rate performance compared with comparative example 1, and it is very big to illustrate that hollow structure has high rate performance
Castering action；Embodiment 1 has similar high rate performance compared with comparative example 2, but cycle performance is far superior to embodiment 2,
Illustrate that niobium doping has very significant improvement result to cycle performance；Embodiment 1 has similar circulation compared with comparative example 3
Performance, but high rate performance is better than comparative example 3, illustrates to coat the effect that also has greatly improved to cycle performance；Embodiment 1 and implementation
Example 2 is compared, and high rate performance and cycle performance difference are little, illustrate different cladding modes be not on the influence of the performance of material it is very big,
Or the present invention does not evaluate larger difference (since result is very approximate, so no longer showing data)；Embodiment 1 and embodiment
3 comparison high rate performances and cycle performance difference are little, show niobium doping and tantalum doping on the performance of material influence less (due to
As a result very approximate, so no longer showing data).
The Applicant declares that the present invention is explained by the above embodiments, the present invention is made is further described, cannot
Assert that specific implementation of the invention is only limited to these instructions.It should be bright for those skilled in the art
, under the early periods for not departing from present inventive concept, several simple deductions or substitution are made to the present invention, all fall within guarantor of the invention
It protects within range and the open scope.
Claims (10)
1. a kind of high magnification long circulating performance multi-element composite positive pole material, it is characterised in that: the positive electrode is D50 2~7
The hollow structure ball of micron, chemical formula LixNiyCozMn1-y-zO2；Doped with the Z chemical combination of mass ratio 0.02%~1% inside it
Object, Z are at least one of Nb or Ta；Its surface, which is coated with, accounts for aluminium compound of the substrate quality than 0.01%~1%；Describedization
In formula, x, y, z is the value of the molar ratio of coherent element, respectively 0.9 < x < 1.3,0.2≤y < 1,0 < z < 0.5, y+z≤1.
2. a kind of preparation method of high magnification long circulating performance multi-element composite positive pole material as described in claim 1, feature
It is, comprising the following steps:
(1) carbon core-C core NiyCozMn1-y-z(OH)2The preparation of presoma:
Compound concentration be 0.01wt%~0.5wt% finely dispersed carbon ball liquid solution, wherein the D50 of carbon ball body be 0.01~
1 μm, then by soluble nickel source compound, cobalt source compound and manganese source compound by Ni:Co:Mn=y:z:(1-y-z) rub
You are 1~3mol/L than being made into mixed solution A, the concentration of mixed solution A；Configuration concentration is the NaOH solution B of 4~10mol/L；
Compound concentration is the ammonia spirit C of 4~10mol/L as complexing agent；Tri- kinds of solution of A, B, C are continuously added to respectively with metering pump
Into the reaction vessel with stirring, reaction temperature is maintained at 30~70 DEG C, and pH is maintained at 9~12, mixing speed 200-800r/
The whole process of min, reaction lead to inert gas shielding；Obtained precipitating is filtered, washed after reaction, at 90-180 DEG C
Dry 4-12h；
(2) hollow structure mixes the Li of ZxNiyCozMn1-y-zO2The preparation of basis material:
C core Ni will be obtained in lithium salts and step (1)yCozMn1-y-z(OH)2In molar ratio Li/M be equal to 1.05~1.2 and with
NiyCozMn1-y-z(OH)2The Z compound that mass ratio is 0.02%~1% carries out mixed at high speed, M NiyCozMn1-y-z(OH)2In
Total metal molar number, Z be at least one of Nb or Ta；Uniformly mixed material is sintered in high temperature furnace, atmosphere be containing
Oxygen atmosphere, high temperature furnace are warming up to 300~750 DEG C with the heating rate of 1~5 DEG C/min, keep the temperature 1~6h, then with the heating rate
750~960 DEG C are warming up to, 6~18h is kept the temperature；Material furnace cooling, screening, removes iron at broken, crushing, obtains hollow structure and mixes niobium
LixNiyCozMn1-y-zO2Basis material；
(3) the hollow Li for mixing Z of Al is coatedxNiyCozMn1-y-zO2The preparation of multi-element composite positive pole material；
1. dry method coats aluminium compound；Matrix Li obtained by step (2)xNiyCozMn1-y-zO2With the mass ratio calculated by aluminium content
0.01%~1% nanoscale aluminium compound mixes 3~60min in high speed mixer high speed, wraps aluminium compound uniformly
It overlays on matrix, in the hollow Li for mixing Z that 400-800 DEG C of 4~12h of constant temperature is evenly coatedxNiyCozMn1-y-zO2It is more
First composite positive pole, Z are at least one of Nb or Ta；
2. wet process coats aluminium compound；Matrix Li obtained by step (2)xNiyCozMn1-y-zO2It is dispersed in water, makes its solid content
It is 10%~80%；The aluminium compound that aluminium content is calculated as mass ratio 0.01%~1% is added, quickly stirs 0.2h~4h, fills
Divide reaction；The slurry stirred evenly is added in double helix vacuum dryer or Rotary Evaporators and is dried in vacuo；In 400-800
DEG C 4~12h of constant temperature and the hollow Li for mixing Z being evenly coatedxNiyCozMn1-y-zO2Multi-element composite positive pole material, Z be Nb or
At least one of Ta.
3. a kind of preparation method of high magnification long circulating performance multi-element composite positive pole material according to claim 2, special
Sign is: core balls used in preparation process are that carbosphere, ball-type graphite, carbon ball, fullerene are one such or a variety of.
4. a kind of preparation method of high magnification long circulating performance multi-element composite positive pole material according to claim 2, special
Sign is: core mean diameter of a ball D50 used in preparation process is 0.01~1 micron；The C core NiyCozMn1-y-z(OH)2
The average diameter D50 of presoma is at 2~7 microns；The Li/M molar ratio is 1.05~1.2, M NiyCozMn1-y-z(OH)2
The middle metalliferous total metal molar number of institute.
5. a kind of preparation method of high magnification long circulating performance multi-element composite positive pole material according to claim 2, special
Sign is: the nickel source compound is one of nickel sulfate, nickel chloride, nickel nitrate, nickel acetate, chloric acid nickel or a variety of；Cobalt source
Compound is one of cobaltous sulfate, cobalt chloride, cobalt nitrate, cobaltous chlorate or a variety of；Manganese source compound be manganese sulfate, manganese chloride,
One of manganese nitrate, manganous bromide are a variety of；The lithium salts, using a kind of or more in lithium carbonate, monohydrate lithium hydroxide, lithium nitrate
Kind.
6. a kind of preparation method of high magnification long circulating performance multi-element composite positive pole material according to claim 2, special
Sign is: adulterating the Z compound, Z is at least one of Nb or Ta, and the niobium compound of use has niobium pentaoxide, dioxy
Change niobium, columbium sesquioxide, columbium dioxide, columbium pentachloride, one or more in niobium (Nb) pentafluoride, and is not limited to above-mentioned containing niobium
Close object；The tantalum compound of use has tantalum pentoxide, tantalum dioxide, three two tantalums of oxidation, tantalum dioxide, tantalic chloride, five fluorinations
It is one or more in tantalum, and it is not limited to the above-mentioned niobium compound that contains, doping is calculated in 0.02~1wt% by the content of Z；
The hollow structure for being evenly coated Al mixes the Li of ZxNiyCozMn1-y-zO2Multi-element composite positive pole material average grain diameter is micro- 2~7
Rice, Z are at least one of Nb or Ta.
7. a kind of preparation method of high magnification long circulating performance multi-element composite positive pole material according to claim 2, special
Sign is: 1. aluminium compound described in dry method cladding, using a kind of or more in aluminium oxide, aluminium hydroxide, aluminum phosphate, aluminum fluoride
Kind, covering amount is in 0.01~1wt%, by Mass Calculation contained by wherein aluminium；2. aluminium compound described in wet process cladding, use are different
Aluminium propoxide, aluminum oxyhydroxide, aluminum nitrate, aluminium chloride, alumina fluid dispersion, aluminum phosphate dispersion liquid one or more of them, aluminium
Covering amount is in 0.01~1wt%, by Mass Calculation contained by wherein aluminium.
8. a kind of preparation method of high magnification long circulating performance multi-element composite positive pole material according to claim 2, special
Sign is: in step (3) 1. in coating equipment used be high speed mixer, the cladding time is 3~60min, coats speed and is
500~2000r/min, temperature of plate are 10~80 DEG C.
9. in a kind of preparation method of the nickelic multi-element composite positive pole material of high circulation performance according to claim 2,
Be characterized in that: (3) step 2. in the solid content of material and solvent be 10~80%, 10 DEG C~70 DEG C of feed liquid temperature, time 10min
~4h, 100~1000r/min of mixing speed.
10. a kind of preparation method of high magnification long circulating performance multi-element composite positive pole material according to claim 2, special
Sign is that the dry purpose of the 2. middle double helix vacuum drying or Rotary Evaporators in step (3) is to accelerate rate of drying
And guarantees that aluminium keeps good being evenly coated property in the process of drying, be also avoided that Li in material+Loss, influence material
Chemical property.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811598179.XA CN109888197B (en) | 2018-12-26 | 2018-12-26 | High-rate long-cycle-performance multi-element composite cathode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811598179.XA CN109888197B (en) | 2018-12-26 | 2018-12-26 | High-rate long-cycle-performance multi-element composite cathode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109888197A true CN109888197A (en) | 2019-06-14 |
| CN109888197B CN109888197B (en) | 2021-12-10 |
Family
ID=66925238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811598179.XA Active CN109888197B (en) | 2018-12-26 | 2018-12-26 | High-rate long-cycle-performance multi-element composite cathode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109888197B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111689528A (en) * | 2020-07-10 | 2020-09-22 | 湖北亿纬动力有限公司 | Ternary material precursor and preparation method and application thereof |
| CN113851633A (en) * | 2021-11-29 | 2021-12-28 | 中南大学 | Niobium-doped high-nickel ternary cathode material coated with niobium phosphate and preparation method thereof |
| CN115036475A (en) * | 2022-05-31 | 2022-09-09 | 四川大学 | High-nickel layered cathode material with radial texture morphology and preparation method thereof |
| CN116947123A (en) * | 2023-09-18 | 2023-10-27 | 四川新能源汽车创新中心有限公司 | Modified positive electrode material and preparation method and application thereof |
| CN117342631A (en) * | 2023-12-05 | 2024-01-05 | 宁德时代新能源科技股份有限公司 | Ternary precursor, preparation method thereof, secondary battery and power utilization device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104319386A (en) * | 2014-09-19 | 2015-01-28 | 青岛乾运高科新材料股份有限公司 | Lithium ion battery cathode multicomponent material and preparation method thereof |
| CN107293744A (en) * | 2016-04-12 | 2017-10-24 | 河南科隆新能源股份有限公司 | A kind of high voltage class monocrystalline tertiary cathode material and preparation method thereof |
| CN108221051A (en) * | 2017-12-11 | 2018-06-29 | 山东零壹肆先进材料有限公司 | Nickelic nickel-cobalt-manganese ternary monocrystal material, preparation method and applications |
| CN109052490A (en) * | 2018-07-09 | 2018-12-21 | 华中科技大学 | A kind of ternary cathode material of lithium ion battery and preparation method thereof |
-
2018
- 2018-12-26 CN CN201811598179.XA patent/CN109888197B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104319386A (en) * | 2014-09-19 | 2015-01-28 | 青岛乾运高科新材料股份有限公司 | Lithium ion battery cathode multicomponent material and preparation method thereof |
| CN107293744A (en) * | 2016-04-12 | 2017-10-24 | 河南科隆新能源股份有限公司 | A kind of high voltage class monocrystalline tertiary cathode material and preparation method thereof |
| CN108221051A (en) * | 2017-12-11 | 2018-06-29 | 山东零壹肆先进材料有限公司 | Nickelic nickel-cobalt-manganese ternary monocrystal material, preparation method and applications |
| CN109052490A (en) * | 2018-07-09 | 2018-12-21 | 华中科技大学 | A kind of ternary cathode material of lithium ion battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 邹邦坤等: "锂离子电池三元正极材料的研究进展", 《中国科学：化学》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111689528A (en) * | 2020-07-10 | 2020-09-22 | 湖北亿纬动力有限公司 | Ternary material precursor and preparation method and application thereof |
| CN113851633A (en) * | 2021-11-29 | 2021-12-28 | 中南大学 | Niobium-doped high-nickel ternary cathode material coated with niobium phosphate and preparation method thereof |
| CN113851633B (en) * | 2021-11-29 | 2022-04-08 | 中南大学 | Niobium-doped high-nickel ternary cathode material coated with niobium phosphate and preparation method thereof |
| CN115036475A (en) * | 2022-05-31 | 2022-09-09 | 四川大学 | High-nickel layered cathode material with radial texture morphology and preparation method thereof |
| CN116947123A (en) * | 2023-09-18 | 2023-10-27 | 四川新能源汽车创新中心有限公司 | Modified positive electrode material and preparation method and application thereof |
| CN116947123B (en) * | 2023-09-18 | 2023-11-21 | 四川新能源汽车创新中心有限公司 | Modified positive electrode material and preparation method and application thereof |
| CN117342631A (en) * | 2023-12-05 | 2024-01-05 | 宁德时代新能源科技股份有限公司 | Ternary precursor, preparation method thereof, secondary battery and power utilization device |
| CN117342631B (en) * | 2023-12-05 | 2024-04-12 | 宁德时代新能源科技股份有限公司 | Ternary precursor, preparation method thereof, secondary battery and power utilization device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109888197B (en) | 2021-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109980219B (en) | Full-gradient nickel-cobalt-manganese positive electrode material, ruthenium oxide coating material and preparation method thereof | |
| CN108091843B (en) | Lithium-rich manganese-based composite cathode material with core-shell structure and preparation method thereof | |
| CN109659542B (en) | High-voltage lithium cobalt oxide cathode material with core-shell structure and preparation method thereof | |
| JP5415008B2 (en) | Non-aqueous electrolyte secondary battery active material and non-aqueous electrolyte secondary battery | |
| CN109888197A (en) | A kind of high magnification long circulating performance multi-element composite positive pole material and preparation method thereof | |
| Lei et al. | Nb-doping in LiNi0. 8Co0. 1Mn0. 1O2 cathode material: Effect on the cycling stability and voltage decay at high rates | |
| CN102214819B (en) | Method for manufacturing cobalt nickel lithium manganate oxide as gradient anode active material of lithium ion battery | |
| CN112599749B (en) | High-entropy oxide lithium ion battery cathode material with high conductivity and preparation method thereof | |
| CN102244236A (en) | Method for preparing lithium-enriched cathodic material of lithium ion battery | |
| CN109546123A (en) | Vanadic anhydride coated core-shell structure gradient nickel cobalt manganese anode material and preparation method | |
| CN104253267A (en) | Carbon-clad spinel lithium titanate material, production method and application thereof | |
| US20210221702A1 (en) | A Lithium-Rich Layered Oxide Material With Phase Structure Gradient And Its Preparation Method | |
| WO2015039490A1 (en) | Lithium-rich anode material and preparation method thereof | |
| CN102034967A (en) | Coprecipitation preparation method of nickel manganese lithium oxide of anode material of high-voltage lithium battery | |
| CN110233261B (en) | Preparation method of single crystal ternary lithium battery positive electrode material and lithium ion battery | |
| CN114843469B (en) | MgFe 2 O 4 Modified P2/O3 type nickel-based layered sodium ion battery positive electrode material and preparation method thereof | |
| CN103022471B (en) | Improve the method for nickelic tertiary cathode material chemical property | |
| CN109088067A (en) | A kind of preparation method of low cobalt doped spinel-layer structure nickel ion doped two-phase composite positive pole | |
| CN112038615A (en) | Lithium-rich manganese-based composite cathode material and preparation method and application thereof | |
| CN113788500A (en) | Surface modification method of lithium-rich manganese-based positive electrode material and lithium-rich manganese-based positive electrode material | |
| CN115312698A (en) | Sodium ion battery layered oxide positive electrode material, preparation method and application | |
| CN109461930B (en) | Gradient-structured multi-component material for lithium ion battery and preparation method thereof | |
| CN109755530B (en) | Surface coating method for titanium barium bimetallic oxide of high-pressure lithium cobalt oxide positive electrode material | |
| CN107768628B (en) | Lithium ion battery anode material and preparation method thereof | |
| CN103456945A (en) | Preparation method of low-cost lithium ion battery anode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |