CN110534717A - Positive electrode and preparation method thereof - Google Patents
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Abstract
The present invention provides a kind of positive electrode, and the chemical formula of the positive electrode is Li1.01~1.12NixCoyMn(1‑x‑y)M0.001~ 0.008B0.001~0.015O2, wherein one or more of 0.45 < x < 0.75,0.15 < y < 0.35,0 < x+y < 1, M Al, Ti, Sn, Nb, the positive electrode include lithium nickel cobalt manganese oxide matrix and the LiMO that is coated on the lithium nickel cobalt manganese oxide matrix2‑B2O3Glassy state compound coating layer.The present invention also provides the preparation methods of above-mentioned positive electrode.The preparation method equipment requirement is low, preparation process is simple, is pure dry way process, is easy to industrialization promotion and application.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries technical fields, in particular to a kind of to have glassy state conductor clad
Positive electrode and preparation method thereof.
Background technique
Lithium ion battery is widely used in the driving power, electronic of portable electronics as a kind of novel green energy resource
The accumulation power supply of automobile power source and solar energy renewable energy.Currently, the restraining factors of lithium ion battery are its cyclic process
In adjoint capacity attenuation, and thus lead to poor cycle life.On the one hand the reason of capacity attenuation is nickel cobalt manganese oxidation
Irreversible change gradually occurs as the cycle progresses for the intrinsic structure of active substances, is on the other hand to work as nickel, cobalt and manganese oxide
When active material takes off lithium, oxidisability enhancing is easy that side reaction occurs with organic electrolyte, to make nickel, cobalt and manganese oxide active matter
Matter loss, leads to capacity attenuation.Therefore, how research inhibits the pernicious phase interaction between lithium nickel cobalt manganese oxide and electrolyte
With raising nickel, cobalt and manganese oxide active material is the key that improve cycle life of lithium ion battery in the stability of circulating battery.
To solve the above-mentioned problems, need to be doped lithium nickel cobalt manganese oxide modified or surface modification coating modification,
Wherein surface cladding is that a kind of comparison is mild, effective modified method.Li2O-2B2O is a kind of very with the table of research potential
The material of face coating decoration, has a biggish forbidden bandwidth and stronger B-O makes its chemical stability in acid condition
It is very excellent.Secondly Li2O-2B2O is a kind of vitreous material with tridimensional network, can permit passing through for ion.This
Kind of feature makes it be the making material of a kind of very important solid electrolyte or as a kind of promotion ionic conductivity
Additive.Due to biggish bandwidth, the ion transmission channel of higher chemical stability and three-dimensional, so that it is also
A kind of extremely potential face finish material for solving the problems, such as high voltage lithium nickel cobalt manganese oxide.
Chinese patent application CN108878861A proposes the method and its lithium of a kind of lithium nickel cobalt manganese oxide surface reconditioning
Nickel, cobalt and manganese oxide is to coat to have in lithium nickel cobalt manganese oxide substrate surface by simple water phase cladding-high-temperature tempering process
There is the mesoporous boron phosphate aluminium layer of high speed lithium ion tunnel, to obtain the lithium nickel cobalt manganese oxide of surface reconditioning.This method obtains
Lithium nickel cobalt manganese oxide have good high voltage cycle stability, higher capacity usage ratio.In the related application,
Cladding means are selection wet process claddings, although can guarantee the uniformity of clad, are increased in actual industrial production
Cost, process is more complicated is unfavorable for industrial applications.
Summary of the invention
Based on the above the deficiencies in the prior art, the present invention intends to provide one kind to obtain high rate capability and cyclicity
The positive electrode of energy, and it is easy to the preparation method of industrial applications and the positive electrode with high rate capability and cycle performance.
The present invention provides a kind of positive electrode, and the chemical formula of the positive electrode is Li1.01~1.12NixCoyMn(1-x-y)
M0.001~0.008B0.001~0.015O2, wherein one in 0.45 < x < 0.75,0.15 < y < 0.35,0 < x+y < 1, M Al, Ti, Sn, Nb
Kind is several, and the positive electrode includes lithium nickel cobalt manganese oxide matrix and is coated on the lithium nickel cobalt manganese oxide matrix
LiMO2-B2O3Glassy state compound coating layer.
The present invention also provides the preparation methods of above-mentioned positive electrode comprising following steps: by lithium salts and nickel cobalt manganese hydrogen-oxygen
Compound presoma uniformly mixes, and lithium nickel cobalt manganese oxide matrix is obtained after high temperature sintering；By the lithium nickel cobalt manganese oxide matrix
In the metallic compound investment ball grinder containing M, 1~3h of ball milling mixing is carried out, obtains being coated with metal after being heat-treated for the first time
The lithium nickel cobalt manganese oxide of oxidation film coats matrix, one or more of M Al, Ti, Sn, Nb；Gold is coated with by described
The lithium nickel cobalt manganese oxide cladding matrix for belonging to oxidation film uniformly mixes in high speed mixer with boron-containing compound, incorporation time
For 5~15min, obtain after second of heat treatment with LiMO2-B2O3Glassy state compound coating film positive electrode.
Method for preparing anode material provided by the invention, whole process the selection of material is cheap and easy to get, equipment requirement is low, prepared
Journey is simple, is pure dry way process, is easy to industrialization promotion and application.Using made from the preparation method have LiMO2-B2O3
Glassy state compound coating layer positive electrode, 3C/0.1C multiplying power discharging specific capacity conservation rate reaches 94%, and circulation is held within 50 weeks
Conservation rate is measured still up to 96%, cycle performance is superior.
Detailed description of the invention
Fig. 1 is the SEM figure of the positive electrode of the embodiment of the present invention 1.
Fig. 2 is the SEM figure of the positive electrode of the embodiment of the present invention 2.
Fig. 3 is the SEM figure of the positive electrode of comparative example 1 of the present invention.
Fig. 4 is button of the battery at 3.0~4.3V made of the positive electrode of the embodiment of the present invention 1 and comparative example 1,2
Circulating battery figure.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with attached drawing embodiment, it is clear that retouched
The embodiment stated is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, originally
Field those of ordinary skill every other embodiment obtained without making creative work, belongs to the present invention
The range of protection.In the absence of conflict, the feature in following embodiment and embodiment can be combined with each other.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
The present invention provides a kind of preparation method of positive electrode comprising following steps:
S1: lithium salts is uniformly mixed with nickel cobalt manganese hydroxide precursor, lithium nickel cobalt manganese oxide is obtained after high temperature sintering
Matrix.
The molar ratio of the lithium salts and the nickel cobalt manganese hydroxide precursor is 1.01~1.12:1.The lithium salts is selected from
One of lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate are a variety of.The chemical formula of the nickel cobalt manganese hydroxide precursor
For NixCoyMn(1-x-y)(OH)2, wherein 0.45 < x < 0.75,0.15 < y < 0.35,0 < x+y < 1.Before the nickel cobalt manganese hydroxide
The average grain diameter D50 for driving body is 2~5um, and the BET specific surface area of the nickel cobalt manganese hydroxide precursor is 5~20m2/g。
Preferably, lithium salts is added in high-speed mixer with nickel cobalt manganese hydroxide precursor and is uniformly mixed, obtained
To powder.The revolving speed of high speed mixer is 900~1200rpm/min, and incorporation time is 10~30min.
The detailed process of high temperature sintering are as follows: put into the powder in sintering furnace, in the air or oxygen atmosphere of sintering furnace
Under with the speed of 1~8 DEG C/min be warming up to 650~750 DEG C, after being then warming up to 850~950 DEG C with the speed of 1~3 DEG C/min
5~15h is kept the temperature, room temperature is finally down to the speed of 60~120 DEG C/h.
It is understood that step S1 is further comprising the steps of: the powder after high temperature sintering being carried out cooling, dissociates crushing
After obtain the lithium nickel cobalt manganese oxide matrix.
S2: the lithium nickel cobalt manganese oxide matrix being put into ball grinder with the metallic compound containing M and carries out ball milling, and first
The lithium nickel cobalt manganese oxide cladding matrix for being coated with metal oxide film is obtained after secondary heat treatment, M is at least in Al, Ti, Sn, Nb
One or more.
The metallic compound containing M is aluminum nitrate, aluminium acetate, aluminium hydroxide, aluminum oxyhydroxide, titanium dioxide, hydrogen-oxygen
Change one or more of titanium, tin oxide, niobium pentaoxide.The metallic compound and the lithium nickel cobalt manganese oxide matrix
Molar ratio is 0.001~0.008:1.Ball-milling Time is 1~3h.Ratio of grinding media to material is 1.3:1.First time heat treatment temperature be 600~
900 DEG C, first time heat treatment time is 8~16h.
One or more M metallic compounds are coated in the nickel, cobalt and manganese oxide matrix surface by dry blending, through heat
Metal oxide coating film, which is generated, in nickel, cobalt and manganese oxide matrix surface after processing obtains the lithium nickel cobalt manganese oxide cladding base
Body reduces the side reaction as caused by HF in electrolyte, improves the cyclical stability of positive electrode at normal temperature.
It is understood that step S2 is further comprising the steps of: carrying out cooled sieve after first time is heat-treated and obtain institute
State the lithium nickel cobalt manganese oxide cladding matrix for being coated with metal oxide film.
S3: by the lithium nickel cobalt manganese oxide cladding matrix for being coated with metal oxide film and boron-containing compound in high speed
It is uniformly mixed in batch mixer, obtains the positive electrode after second of heat treatment.
The boron-containing compound is boric acid, metaboric acid, pyroboric acid (H2B4O7), one of boron oxide.The boracic chemical combination
The molar ratio of object and lithium nickel cobalt manganese oxide cladding matrix is 0.001~0.015:1.Incorporation time is 5~15min.The
Secondary heat treatment temperature is 300~600 DEG C, and second of heat treatment time is 4~12h.
Lithium nickel cobalt manganese oxide cladding matrix and boron-containing compound are subjected to secondary dry blending cladding, it is thermally treated
After form Li2O-2B2O3Clad, clad ion conductivity with higher, fusing point is low, and in melting, viscosity is lower,
The positive electrode surface of formation is relatively smooth, can contact with conductive agent, conducive to the transmission of lithium ion, effectively improve just well
High rate performance, cycle performance, storage performance and the security performance of pole material.
The preparation method of positive electrode provided by the invention, by the way that dry method cladding is collectively formed twice on the surface of the material
LiMO2-B2O3Glassy state compound coating layer, can not only reduce the direct contact area of positive electrode and electrolyte, reduce electricity
The HF in liquid is solved to the corrosiveness of positive electrode, the electronic conductivity of positive electrode is improved, improves high rate performance；It can also subtract
Small internal resistance reduces polarization loss, further promotes the cycle performance of positive electrode.In addition, whole process the selection of material it is cheap and easy to get,
Equipment requirement is low, preparation process is simple, is pure dry way process, is easy to industrialization promotion and application.
The present invention provides a kind of positive electrode prepared using above-mentioned preparation method.The positive electrode includes lithium nickel cobalt manganese
Oxide matrix and the LiMO being coated on the lithium nickel cobalt manganese oxide matrix2-B2O3Glassy state compound coating layer.It is described
The chemical formula of positive electrode is Li1.01~1.12NixCoyMn(1-x-y)M0.001~0.008B0.001~0.015O2, wherein 0.45 < x < 0.75,
One or more of 0.15 < y < 0.35,0 < x+y < 1, M Al, Ti, Sn, Nb.The LiMO2-B2O3The compound packet of glassy state
Coating with a thickness of 30~80nm.
In the contact position of the positive electrode and electrolyte, the LiMO2-B2O3Glassy state compound coating layer can fill
When the effect of protective layer, alleviate the dissolution of electrolyte oxygenolysis under high voltages and active material.Former Zhou Xunhuan's
In the process, since the effect of electrochemistry stress makes the LiMO as clad2-B2O3A kind of network frame with Three-dimensional Open
Structure, this structure can accommodate the Li of some movements+, and then one kind is formed more resistant to chemical attack and tool during circulation
There is the LiMO of more preferable ionic conductivity2-B2O3Interface, and this interfacial layer is the main component of solid electrolyte membrane (SEI), this
Li during charge and discharge cycles later, at solid liquid interface is promoted accordingly+Diffusion and transmission.Due to
LiMO2-B2O3The effect of clad, the high rate performance and cycle performance of the lithium nickel cobalt manganese oxide after compound coating can
It is significantly improved and transmits.
The present invention is specifically described below by embodiment and comparative example.
Embodiment 1
By lithium hydroxide and nickel cobalt manganese hydroxide precursor (chemical formula Ni0.60Co0.20Mn0.20(OH)2) according to molar ratio
1.08:1 is added in high-speed mixer, and wherein the average grain diameter D50 of presoma is 2~5um, the BET specific surface area of presoma
For 5~20m2/g.With the powder that is obtained after revolving speed 900rpm/min mixing 20min under the air atmosphere of sintering furnace with 4 DEG C/
The speed of min is warming up to 730 DEG C, is then warming up to after 950 DEG C with the speed of 3 DEG C/min and keeps the temperature 12h, finally with 100 DEG C/h's
Speed is cooled to room temperature dissociation crushing and obtains lithium nickel cobalt manganese oxide matrix Li1.08Ni0.6Co0.2Mn0.2O2.By lithium nickel cobalt manganese
Poly- ammonia is added by ratio of grinding media to material 1.3:1 according in molar ratio 1:0.001 investment ball grinder in object matrix and aluminum oxyhydroxide (AlOOH)
Ester ball keeps the temperature 12h after carrying out ball milling mixing 2h at 700 DEG C, is sieved after cooling and obtains lithium nickel cobalt manganese oxide cladding matrix
Li1.08Ni0.6Co0.2Mn0.2Al0.001O2.By lithium nickel cobalt manganese oxide cladding matrix and white metaboric acid (HBO2) according to molar ratio
1:0.002 is uniformly mixed in high speed mixer, incorporation time 10min, obtains same lithium nickel cobalt manganese oxide solid colour
For the powder mixture of black gray expandable.Then 8h, the lithium after glassy state conductor cladding is obtained after being sieved after cooling are kept the temperature at 450 DEG C
Nickel, cobalt and manganese oxide Li1.08Ni0.6Co0.2Mn0.2Al0.001B0.002O2。
Embodiment 2
By lithium hydroxide and nickel cobalt manganese hydroxide precursor (chemical formula Ni0.60Co0.20Mn0.20(OH)2) according to molar ratio
1.08:1 is added in the high-speed mixer of revolving speed 1200rpm/min, air of the powder obtained after mixing 20min in sintering furnace
730 DEG C are warming up to the speed of 3.5 DEG C/min under atmosphere, is then warming up to after 945 DEG C with the speed of 3 DEG C/min and keeps the temperature 12h, most
Dissociation crushing is cooled to room temperature with the speed of 100 DEG C/h afterwards and obtains lithium nickel cobalt manganese oxide matrix Li1.08Ni0.6Co0.2Mn0.2O2。
By lithium nickel cobalt manganese oxide matrix and aluminium hydroxide according in molar ratio 1:0.0015 investment ball grinder, add by ratio of grinding media to material 1.3:1
Enter after polyurethane ball carries out ball milling mixing 2h and keep the temperature 10h at 650 DEG C, is sieved after cooling and obtains black gray expandable lithium nickel cobalt manganese oxide
Coat matrix Li1.08Ni0.6Co0.2Mn0.2Al0.0015O2.Black gray expandable lithium nickel cobalt manganese oxide is coated into matrix and pyroboric acid
(H2B4O7) uniformly mixed in high speed mixer according to molar ratio 1:0.4, then incorporation time 10min is protected at 460 DEG C
Warm 8h, the lithium nickel cobalt manganese oxide Li being sieved after glassy state conductor cladding can be obtained after cooling1.08Ni0.6Co0.2Mn0.2
Al0.0015B0.003O2。
Embodiment 3
By lithium hydroxide and nickel cobalt manganese hydroxide precursor (chemical formula Ni0.60Co0.20Mn0.20(OH)2) according to molar ratio
1.08:1 is added in the high-speed mixer of revolving speed 1000rpm/min, air of the powder obtained after mixing 20min in sintering furnace
730 DEG C are warming up to the speed of 3 DEG C/min under atmosphere, is then warming up to after 935 DEG C with the speed of 3 DEG C/min and keeps the temperature 12h, finally
Dissociation crushing, which is cooled to room temperature, with the speed of 100 DEG C/h obtains lithium nickel cobalt manganese oxide matrix Li1.08Ni0.6Co0.2Mn0.2O2.It will
Lithium nickel cobalt manganese oxide matrix and titanium dioxide are added according in molar ratio 1:0.0023 investment ball grinder by ratio of grinding media to material 1.3:1
Polyurethane ball keeps the temperature 12h after carrying out ball milling mixing 2h at 600 DEG C, is sieved after cooling and obtains lithium nickel cobalt manganese oxide cladding matrix
Li1.08Ni0.6Co0.2Mn0.2Ti0.0023O2.Lithium nickel cobalt manganese oxide is coated matrix and boron oxide to exist according to molar ratio 1:0.0035
It is uniformly mixed in high speed mixer, incorporation time 10min, 8h is then kept the temperature at 440 DEG C, being sieved after cooling can be obtained glass
Lithium nickel cobalt manganese oxide Li after glass state conductor cladding1.08Ni0.6Co0.2Mn0.2Ti0.0023B0.0035O2。
Embodiment 4
By lithium hydroxide and nickel cobalt manganese hydroxide precursor (chemical formula Ni0.60Co0.20Mn0.20(OH)2) according to molar ratio
1.08:1 is added in the high-speed mixer of revolving speed 950rpm/min, air of the powder obtained after mixing 20min in sintering furnace
730 DEG C are warming up to the speed of 3 DEG C/min under atmosphere, is then warming up to after 930 DEG C with the speed of 3 DEG C/min and keeps the temperature 12h, finally
Dissociation crushing, which is cooled to room temperature, with the speed of 100 DEG C/h obtains lithium nickel cobalt manganese oxide matrix Li1.08Ni0.6Co0.2Mn0.2O2.It will
Poly- ammonia is added by ratio of grinding media to material 1.3:1 according in molar ratio 1:0.004 investment ball grinder in lithium nickel cobalt manganese oxide matrix and tin oxide
Ester ball keeps the temperature 12h after carrying out ball milling mixing 2h at 700 DEG C, is sieved after cooling and obtains lithium nickel cobalt manganese oxide cladding matrix
Li1.08Ni0.6Co0.2Mn0.2Sn0.004O2.Lithium nickel cobalt manganese oxide is coated matrix and metaboric acid to exist according to molar ratio 1:0.004
It is uniformly mixed in high speed mixer, incorporation time 10min, 8h is then kept the temperature at 420 DEG C, being sieved after cooling can be obtained glass
Lithium nickel cobalt manganese oxide Li after glass state conductor cladding1.08Ni0.6Co0.2Mn0.2Sn0.004B0.004O2。
Embodiment 5
By lithium hydroxide and nickel cobalt manganese hydroxide precursor (chemical formula Ni0.60Co0.20Mn0.20(OH)2) according to molar ratio
1.08:1 is added in the high-speed mixer of revolving speed 1100rpm/min, air of the powder obtained after mixing 20min in sintering furnace
730 DEG C are warming up to the speed of 3 DEG C/min under atmosphere, is then warming up to after 925 DEG C with the speed of 3 DEG C/min and keeps the temperature 10h, finally
Dissociation crushing, which is cooled to room temperature, with the speed of 100 DEG C/h obtains lithium nickel cobalt manganese oxide matrix Li1.08Ni0.6Co0.2Mn0.2O2.It will
Lithium nickel cobalt manganese oxide matrix and aluminium acetate are added poly- according in molar ratio 1:0.0043 investment ball grinder by ratio of grinding media to material 1.3:1
Urethane ball keeps the temperature 12h after carrying out ball milling mixing 2h at 580 DEG C, is sieved after cooling and obtains lithium nickel cobalt manganese oxide cladding matrix
Li1.08Ni0.6Co0.2Mn0.2Al0.0043O2.Lithium nickel cobalt manganese oxide is coated matrix and boron oxide to exist according to molar ratio 1:0.005
It is uniformly mixed in high speed mixer, incorporation time 10min, 8h is then kept the temperature at 400 DEG C, being sieved after cooling can be obtained glass
Lithium nickel cobalt manganese oxide Li after glass state conductor cladding1.08Ni0.6Co0.2Mn0.2Al0.0043B0.005O2。
Comparative example 1
By lithium hydroxide and nickel cobalt manganese hydroxide precursor (chemical formula Ni0.60Co0.20Mn0.20(OH)2) according to molar ratio
1.08:1 is added in the high-speed mixer of revolving speed 1200rpm/min, air of the powder obtained after mixing 20min in sintering furnace
730 DEG C are warming up to the speed of 3 DEG C/min under atmosphere, is then warming up to after 940 DEG C with the speed of 3 DEG C/min and keeps the temperature 12h, finally
Dissociation crushing, which is cooled to room temperature, with the speed of 100 DEG C/h obtains the lithium nickel cobalt manganese oxide of no surface modification
Li1.08Ni0.60Co0.20Mn0.20O2。
Comparative example 2
By lithium hydroxide and nickel cobalt manganese hydroxide precursor (chemical formula Ni0.60Co0.20Mn0.20(OH)2) according to molar ratio
1.08:1 is added in the high-speed mixer of revolving speed 1200rpm/min, air of the powder obtained after mixing 20min in sintering furnace
730 DEG C are warming up to the speed of 3 DEG C/min under atmosphere, is then warming up to after 940 DEG C with the speed of 3 DEG C/min and keeps the temperature 12h, finally
Dissociation crushing, which is cooled to room temperature, with the speed of 100 DEG C/h obtains lithium nickel cobalt manganese oxide matrix Li1.08Ni0.6Co0.2Mn0.2O2.It will
Lithium nickel cobalt manganese oxide matrix and aluminum oxyhydroxide are added according in molar ratio 1:0.002 investment ball grinder by ratio of grinding media to material 1.3:1
Polyurethane ball keeps the temperature 12h after carrying out ball milling mixing 2h at 700 DEG C, is sieved and is obtained only by a lithium for one-time surface cladding after cooling
Nickel, cobalt and manganese oxide Li1.08Ni0.6Co0.2Mn0.2Al0.002O2。
Fig. 1 to Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of 1 gained positive electrode of embodiment 1,2 and comparative example.It is soft with imageJ
Part measures a grain size in figure, and every figure measures 30 points, measures an average crystal grain for the positive electrode of embodiment 1
For 2.77um, the crystal grain that is averaged of the positive electrode of embodiment 2 is 2.83um, and being averaged for the positive electrode of comparative example 1 is primary
Crystal grain is 2.80um.Illustrate that the grain size of positive electrode is controllable, has cladding different with the positive electrode surface topography of no cladding.
There are some additional substances on the positive electrode surface of embodiment 1,2 by cladding, has its surface some fuzzy, this is because
With the presence of caused by clad, gap of the coating between positive electrode surface and colony is distributed on positive electrode surface；And
The positive electrode surface of the comparative example 1 of no cladding, which then shows, is more clear smooth surface profile.
After battery is made in positive electrode obtained by embodiment 1-5 and comparative example 1-2, by button cell tester to electricity
Pond correlation electrochemistry can be carried out test.Table 1 is battery made of positive electrode obtained by embodiment 1-5 and comparative example 1-2
Chemical property 0.1C first discharge specific capacity, 3C/0.1C multiplying power discharging capacity retention ratio, 50 weeks 3C circulation volume conservation rates
Test result.Fig. 4 is button cell of the battery at 3.0~4.3V made of embodiment 1 and comparative example 1,2 gained positive electrodes
Circulation figure.
1 first charge-discharge capacity of table, multiplying power and cycle performance
By test result it can be seen that the embodiment of the present invention 1 to embodiment 5 passes through LiMO2-B2O3Lithium nickel cobalt after cladding
Mn oxide has better processing performance, cyclical stability and high rate performance compared to comparative example material, and powder flowbility improves,
First discharge specific capacity improves obviously, and 3C/0.1C multiplying power discharging specific capacity conservation rate reaches 94%, 50 weeks circulation volume conservation rates
Still up to 96%, cycle performance is superior.And the uncoated any substance of comparative example 1, powder flowbility are poor, for the first time discharge capacity compared with
It is low, and multiplying power and cycle performance are poor, respectively only 90% and 88%；Aluminum oxyhydroxide (AlOOH) cladding is added in comparative example 2,
Powder flowbility, which has, slightly to be promoted, and cycle performance gets a promotion, and close to 92%, but first discharge specific capacity and high rate performance are without bright
It is aobvious to improve.
In addition, those skilled in the art can also do other variations in spirit of that invention, certainly, these are smart according to the present invention
The variation that mind is done should be all included in scope of the present invention.
Claims (10)
1. a kind of positive electrode, which is characterized in that the chemical formula of the positive electrode is Li1.01~1.12NixCoyMn(1-x-y)
M0.001~0.008B0.001~0.015O2, wherein one in 0.45 < x < 0.75,0.15 < y < 0.35,0 < x+y < 1, M Al, Ti, Sn, Nb
Kind is several, and the positive electrode includes lithium nickel cobalt manganese oxide matrix and is coated on the lithium nickel cobalt manganese oxide matrix
LiMO2-B2O3Glassy state compound coating layer.
2. positive electrode as described in claim 1, which is characterized in that the Li1.01~1.12NixCoyMn(1-x-y)M0.001~ 0.008B0.001~0.015O2Including Li1.08Ni0.6Co0.2Mn0.2Al0.001B0.002O2、Li1.08Ni0.6Co0.2Mn0.2Al0.0015B0.003O2、
Li1.08Ni0.6Co0.2Mn0.2Ti0.0023B0.0035O2、Li1.08Ni0.6Co0.2Mn0.2Sn0.004B0.004O2、Li1.08Ni0.6Co0.2Mn0.2
Al0.0043B0.005O2Any one of.
3. the preparation method of any positive electrode in claim 1-2 comprising following steps:
Lithium salts is uniformly mixed with nickel cobalt manganese hydroxide precursor, lithium nickel cobalt manganese oxide matrix is obtained after high temperature sintering；
By the lithium nickel cobalt manganese oxide matrix with the metallic compound investment ball grinder containing M, 1~3h of ball milling mixing is carried out,
Obtain being coated with the lithium nickel cobalt manganese oxide cladding matrix of metal oxide film for the first time after being heat-treated, in M Al, Ti, Sn, Nb
One or more；
By the lithium nickel cobalt manganese oxide cladding matrix for being coated with metal oxide film and boron-containing compound in high speed mixer
Interior uniform mixing, incorporation time are 5~15min, are obtained after second of heat treatment with LiMO2-B2O3Glassy state compound coating
The positive electrode of film.
4. the preparation method of positive electrode as claimed in claim 3, which is characterized in that the lithium salts is selected from lithium carbonate, hydrogen-oxygen
Change one of lithium, lithium acetate, lithium nitrate or a variety of.
5. the preparation method of positive electrode as claimed in claim 3, which is characterized in that the nickel cobalt manganese hydroxide precursor
Chemical formula be NixCoyMn(1-x-y)(OH)2, wherein 0.45 < x < 0.75,0.15 < y < 0.35,0 < x+y < 1, the nickel cobalt manganese hydrogen
The average grain diameter D50 of oxide precursor is 2~5um, the BET specific surface area of the nickel cobalt manganese hydroxide precursor is 5~
20m2/g。
6. the preparation method of positive electrode as claimed in claim 3, which is characterized in that the metallic compound containing M is nitre
One of sour aluminium, aluminium acetate, aluminium hydroxide, aluminum oxyhydroxide, titanium dioxide, titanium hydroxide, tin oxide, niobium pentaoxide or
It is several.
7. the preparation method of positive electrode as claimed in claim 3, which is characterized in that the boron-containing compound is boric acid, partially
One of boric acid, pyroboric acid, boron oxide.
8. the preparation method of positive electrode as claimed in claim 3, which is characterized in that the lithium salts and the nickel cobalt manganese hydrogen-oxygen
The molar ratio of compound presoma is 1.01~1.12:1, mole of the metallic compound and the lithium nickel cobalt manganese oxide matrix
Than for 0.001~0.008:1.
9. the preparation method of positive electrode as claimed in claim 3, which is characterized in that the high temperature sintering refers in sintering furnace
Air or oxygen atmosphere under with the speed of 1~8 DEG C/min be warming up to 650~750 DEG C, then with the speed liter of 1~3 DEG C/min
Temperature is finally down to room temperature to 5~15h of heat preservation after 850~950 DEG C with the speed of 60~120 DEG C/h.
10. the preparation method of positive electrode as claimed in claim 3, which is characterized in that by lithium salts and nickel cobalt manganese hydroxide
It includes: to be added to lithium salts in high-speed mixer with nickel cobalt manganese hydroxide precursor uniformly to be mixed that presoma, which uniformly mixes,
It closes, the revolving speed of high speed mixer is 900~1200rpm/min, and incorporation time is 10~30min.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111646523A (en) * | 2020-06-29 | 2020-09-11 | 蜂巢能源科技有限公司 | High-safety double-doped high-nickel ternary cathode material, preparation method thereof and lithium ion battery |
| CN112614988A (en) * | 2020-12-15 | 2021-04-06 | 蜂巢能源科技有限公司 | Positive electrode material and preparation method and application thereof |
| CN113328070A (en) * | 2020-06-18 | 2021-08-31 | Sk新技术株式会社 | Positive electrode active material for lithium secondary battery, and method for producing same |
| WO2023016269A1 (en) * | 2021-08-11 | 2023-02-16 | 格林美股份有限公司 | Quaternary positive electrode material and preparation method therefor and application thereof |
| CN117894971A (en) * | 2024-03-18 | 2024-04-16 | 中南大学 | Glassy metal organic framework material modified ternary positive electrode material, and preparation method and application thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130011738A1 (en) * | 2011-07-04 | 2013-01-10 | Microvast New Materials (Huzhou) Co., LTD. | Cathode material of lithium ion secondary battery and method for manufacturing the same |
| KR20140025102A (en) * | 2012-08-21 | 2014-03-04 | 주식회사 엘지화학 | Cathode active material for lithium secondary battery and manufacturing method thereof |
| JP2016039062A (en) * | 2014-08-08 | 2016-03-22 | トヨタ自動車株式会社 | Positive electrode composite material and sulfide all-solid battery arranged by use thereof |
| CN107394170A (en) * | 2017-07-27 | 2017-11-24 | 苏州思创源博电子科技有限公司 | A kind of preparation method of the sulphur lithium anode material of metal oxide cladding |
| CN107425188A (en) * | 2017-07-30 | 2017-12-01 | 苏州思创源博电子科技有限公司 | A kind of preparation method of oxide cladding lithium cobaltate cathode material |
| CN107910534A (en) * | 2017-11-22 | 2018-04-13 | 淮安新能源材料技术研究院 | A kind of nickelic tertiary cathode material preparation method of NCM811 types |
| CN108390039A (en) * | 2018-02-23 | 2018-08-10 | 成都新柯力化工科技有限公司 | A kind of nickelic anode material of lithium battery that double oxide coats altogether and preparation method |
| CN108807926A (en) * | 2018-06-22 | 2018-11-13 | 格林美（无锡）能源材料有限公司 | A kind of Co/B coats nickel cobalt manganese lithium ion anode material and preparation method thereof altogether |
| CN109461928A (en) * | 2018-09-19 | 2019-03-12 | 北京当升材料科技股份有限公司 | A kind of high-energy density polynary positive pole material and preparation method thereof |
| CN109686932A (en) * | 2018-12-12 | 2019-04-26 | 无锡晶石新型能源股份有限公司 | A kind of preparation method by the nickelic tertiary cathode material of polynary coating modification |
| CN109830651A (en) * | 2017-11-23 | 2019-05-31 | 天津国安盟固利新材料科技股份有限公司 | A kind of tertiary cathode high-nickel material and preparation method thereof that double-coating is modified |
| CN109888225A (en) * | 2019-02-27 | 2019-06-14 | 桑顿新能源科技有限公司 | Positive electrode and preparation method thereof and lithium ion battery |
| CN110120505A (en) * | 2019-05-07 | 2019-08-13 | 厦门厦钨新能源材料有限公司 | Anode material for lithium-ion batteries, preparation method and lithium ion battery |
| CN110148712A (en) * | 2018-02-11 | 2019-08-20 | 湖南杉杉能源科技股份有限公司 | A kind of rich lithium manganese anode material and preparation method thereof that compound coating is modified |
-
2019
- 2019-09-04 CN CN201910831610.9A patent/CN110534717B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130011738A1 (en) * | 2011-07-04 | 2013-01-10 | Microvast New Materials (Huzhou) Co., LTD. | Cathode material of lithium ion secondary battery and method for manufacturing the same |
| KR20140025102A (en) * | 2012-08-21 | 2014-03-04 | 주식회사 엘지화학 | Cathode active material for lithium secondary battery and manufacturing method thereof |
| JP2016039062A (en) * | 2014-08-08 | 2016-03-22 | トヨタ自動車株式会社 | Positive electrode composite material and sulfide all-solid battery arranged by use thereof |
| CN107394170A (en) * | 2017-07-27 | 2017-11-24 | 苏州思创源博电子科技有限公司 | A kind of preparation method of the sulphur lithium anode material of metal oxide cladding |
| CN107425188A (en) * | 2017-07-30 | 2017-12-01 | 苏州思创源博电子科技有限公司 | A kind of preparation method of oxide cladding lithium cobaltate cathode material |
| CN107910534A (en) * | 2017-11-22 | 2018-04-13 | 淮安新能源材料技术研究院 | A kind of nickelic tertiary cathode material preparation method of NCM811 types |
| CN109830651A (en) * | 2017-11-23 | 2019-05-31 | 天津国安盟固利新材料科技股份有限公司 | A kind of tertiary cathode high-nickel material and preparation method thereof that double-coating is modified |
| CN110148712A (en) * | 2018-02-11 | 2019-08-20 | 湖南杉杉能源科技股份有限公司 | A kind of rich lithium manganese anode material and preparation method thereof that compound coating is modified |
| CN108390039A (en) * | 2018-02-23 | 2018-08-10 | 成都新柯力化工科技有限公司 | A kind of nickelic anode material of lithium battery that double oxide coats altogether and preparation method |
| CN108807926A (en) * | 2018-06-22 | 2018-11-13 | 格林美（无锡）能源材料有限公司 | A kind of Co/B coats nickel cobalt manganese lithium ion anode material and preparation method thereof altogether |
| CN109461928A (en) * | 2018-09-19 | 2019-03-12 | 北京当升材料科技股份有限公司 | A kind of high-energy density polynary positive pole material and preparation method thereof |
| CN109686932A (en) * | 2018-12-12 | 2019-04-26 | 无锡晶石新型能源股份有限公司 | A kind of preparation method by the nickelic tertiary cathode material of polynary coating modification |
| CN109888225A (en) * | 2019-02-27 | 2019-06-14 | 桑顿新能源科技有限公司 | Positive electrode and preparation method thereof and lithium ion battery |
| CN110120505A (en) * | 2019-05-07 | 2019-08-13 | 厦门厦钨新能源材料有限公司 | Anode material for lithium-ion batteries, preparation method and lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| BIAN XIA FEI，ET AL: ""High-Performance Li(Li0.18Ni0.15Co0.15Mn0.52)O-2@Li4M5O12 Heterostructured Cathode Material Coated with a Lithium Borate Oxide Glass Layer"", 《CHEMISTRY OF MATERIALS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113328070A (en) * | 2020-06-18 | 2021-08-31 | Sk新技术株式会社 | Positive electrode active material for lithium secondary battery, and method for producing same |
| CN111646523A (en) * | 2020-06-29 | 2020-09-11 | 蜂巢能源科技有限公司 | High-safety double-doped high-nickel ternary cathode material, preparation method thereof and lithium ion battery |
| CN112614988A (en) * | 2020-12-15 | 2021-04-06 | 蜂巢能源科技有限公司 | Positive electrode material and preparation method and application thereof |
| CN112614988B (en) * | 2020-12-15 | 2021-10-19 | 蜂巢能源科技有限公司 | Positive electrode material and preparation method and application thereof |
| WO2023016269A1 (en) * | 2021-08-11 | 2023-02-16 | 格林美股份有限公司 | Quaternary positive electrode material and preparation method therefor and application thereof |
| CN117894971A (en) * | 2024-03-18 | 2024-04-16 | 中南大学 | Glassy metal organic framework material modified ternary positive electrode material, and preparation method and application thereof |
| CN117894971B (en) * | 2024-03-18 | 2024-06-04 | 中南大学 | Glassy metal organic framework material modified ternary positive electrode material, and preparation method and application thereof |
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