CN107585794B - The preparation method of tertiary cathode material and the material and its presoma - Google Patents
The preparation method of tertiary cathode material and the material and its presoma Download PDFInfo
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Abstract
The present invention provides a kind of ternary precursors with composite heterogenous junction structure, have following molecular formula composition: Ni1‑a‑bCoaMb(OH)2@Ni1‑x‑yCoxMyOz, wherein 0 < a < 1,0 <b < 1,0 < a+b < 1,0 < x < 1,0 < y < 1,0 < x+y < 1,1 < z < 1.5, M=Mn or Al；The ternary precursor includes ternary oxide presoma and ternary hydroxide presoma, and the ternary hydroxide presoma is coated on ternary oxide presoma surface, the molecular formula of the ternary oxide presoma are as follows: Ni1‑x‑yCoxMyOz, the molecular formula of the ternary hydroxide presoma is Ni1‑a‑bCoaMb(OH)2.The present invention further provides the preparation methods of above-mentioned ternary precursor, this method is combined using spray pyrolysis with coprecipitation, using ternary oxide presoma obtained by spray pyrolysis as crystal seed, one layer of ternary hydroxide presoma is coated on its surface using coprecipitation and prepares tertiary cathode material up to ternary precursor, then with ternary precursor and lithium salts mixed sintering.The tertiary cathode material has good layer structure, higher first charge discharge efficiency, height ratio capacity and excellent circulating ratio performance.
Description
Technical field
The present invention relates to battery material fields, and in particular to a kind of tertiary cathode material, its presoma and the material and preceding
Drive the preparation method of body.
Background technique
As the universal and portable electronic product of 3C electronic product is to super book, fine and multifunction direction development,
Lithium ion battery due to it is high with specific energy, have extended cycle life, operating voltage is high, self discharge is small, memory-less effect, it is small in size,
Light-weight, advantages of environment protection and occupy leading position.One of critical material as lithium ion battery, positive electrode is very
The energy density of lithium ion battery, power density and cycle life are determined in big degree.Stratiform nickle cobalt lithium manganate tertiary cathode
Material combines the low-cost advantage of the excellent cycle performance of cobalt acid lithium, the high capacity characteristics of lithium nickelate, LiMn2O4, and safety
Can be good, there are apparent trielement synergistic effects, become a kind of very with the anode material for lithium-ion batteries of development prospect.
But the tertiary cathode material of different chemical constituent and structures, the inherent shortcoming of equal various degrees, mainly
There are cationic mixing, interface side reaction and structural instability.The physical property and chemical property of tertiary cathode material are very big
It is determined in degree by used preparation method, the synthesis of ternary material at present is divided into the progress of two steps mostly, first using as being co-precipitated
The methods of method, hydro-thermal method, sol-gel method or spray pyrolysis synthesis of ternary presoma, then presoma is mixed with lithium salts
High temperature sintering synthesizes corresponding tertiary cathode material afterwards.Wherein ternary precursor is in appearance structure, particle diameter distribution and tap density
Etc. otherness by subsequent prepared positive electrode physical property and chemical property generate significant impact, before raising
The physical and chemical performance for driving body is particularly critical to tertiary cathode material performance is improved.
Currently, the main stream approach of synthesis of ternary material is first then to be passed through with lithium salts using Co deposited synthesis presoma
High temperature solid state reaction and obtain tertiary cathode material.By regulating and controlling the parameter of coprecipitation reaction, can get has high-tap density,
The good polynary hydroxide precursor of sphericity, thus synthesize regular appearance, the high positive electrode of tap density, but
Prepare nickel cobalt manganese (nickel cobalt aluminium) ternary especially nickelic ternary precursor when, the hydroxide precursor by coprecipitation preparation is living
Property it is not high, generally require can just synthesize using the active stronger Lithium hydroxide monohydrate of higher but corrosivity as lithium source it is good nickelic
Ternary layered positive electrode, while the circulation of material and high rate performance are all lower.Such as the patent of Publication No. CN104810521A
A kind of preparation method of nickle cobalt lithium manganate tertiary cathode material is disclosed, before preparing tertiary cathode material by using coprecipitation
Body is driven, LiOH is added and is sintered to obtain LiNi0.8Co0.15Mn0.05O2, add a certain proportion of LiOH and H3BO3, agitated, steaming
Nickel-cobalt-manganese ternary material after doing, being coated after heat treatment, reversible capacity is low after which recycles 10 times at 0.2C
In 160mAhg-1.The patent of CN101510603 discloses a kind of system of anode material lithium nickle cobalt manganic acid of lithium ion battery
Sulfuric acid mixed salt solution, ammonium hydroxide and the sodium hydroxide solution of nickel, cobalt, manganese are continuously injected into reactor through being co-precipitated by Preparation Method
Nickel-cobalt-manganese ternary presoma is obtained, reacts to obtain Li with lithium salts after being pre-sinteredzNixCoyMnxO2Positive electrode.Using above-mentioned side
The positive electrode specific capacity and high rate performance that method obtains are all lower.Compared to coprecipitation, spray pyrolysis have process it is short, to original
Expect many advantages, such as adaptable, process is simple, high production efficiency.Ternary oxide presoma is prepared using spray pyrolysis, is produced
Product component is uniform, and batch reproducibility is good, and often activity is higher due to the special constructions such as hollow, porous, nucleocapsid for product, after
The synthesis of continuous positive electrode is more simple, and the positive electrode of synthesis has preferable circulating ratio performance.Although spray pyrolysis skill
Art, which prepares positive electrode, to be had many advantages, such as above, but it is easy to produce hollow or crushed particles, leads to prepared positive electrode
Tap density is far below coprecipitation material prepared, this is also that spray pyrolysis technologies is hindered to lead in anode material for lithium-ion batteries
One principal element of domain realization industrial application.As the patent of Publication No. CN106953095A discloses a kind of nickelic stratiform
The preparation method of positive electrode obtains nickel-based oxide presoma by spray pyrolysis, after mixing with lithium carbonate, prepares through sintering
Obtain the nickelic layered cathode material.There is very excellent circulating ratio performance using the positive electrode that this method obtains,
But it is the other random particle of submicron order that existing main problem, which is for material, and first charge discharge efficiency is lower, and only 80% or so,
Tap density is not also high.Mainly hollow bead is crushed by addition various additives and by ball milling in document report at present
Secondary afterwards to make this two approach of bulky grain to improve the tap density of material, these methods can improve anode to a certain extent
The tap density of material, but the requirement of practical application is still not achieved.
Therefore, how i.e. guarantee positive electrode possess excellent circulation and high rate performance have again good layer structure,
High tap density is the problem that researchers encounter.
For technical problem present in above-mentioned description of the prior art, currently no effective solution has been proposed.
Summary of the invention
In order to overcome the shortcomings in the prior art and defect, the present invention provides before a kind of ternary with composite heterogenous junction structure
The tertiary cathode material and their preparation method that body, this ternary precursor synthesize.The present invention uses spray pyrolysis together
The precipitation method combine, with ternary oxide presoma Ni obtained by spray pyrolysis1-x-yCoxMyOz(M=Mn or Al) is crystal seed, is adopted
With coprecipitation in one layer of ternary hydroxide presoma Ni of ternary oxide presoma surface uniform deposition1-a-bCoaMb(OH)2
(M=Mn or Al) is to get Ni1-a-bCoaMb(OH)2@Ni1-x-yCoxMyOz(M=Mn or Al) has composite heterogenous junction structure
Ternary precursor；The present invention is further again with synthesized Ni1-a-bCoaMb(OH)2@Ni1-x-yCoxMyOz(M=Mn or Al) is multiple
It closes heterogeneous presoma and lithium salts mixed sintering prepares LiNi1-a-bCoaMbO2@LiNi1-x-yCoxMyO2(M=Mn or Al) ternary is just
Pole material.The tertiary cathode material prepared through the invention has good layer structure, higher first charge discharge efficiency, height ratio capacity
And excellent circulating ratio performance.
To achieve the above object, the following technical solutions are proposed by the present invention:
Present invention firstly provides a kind of ternary precursors with composite heterogenous junction structure, which is characterized in that has following
Molecular formula composition: Ni1-a-bCoaMb(OH)2@Ni1-x-yCoxMyOz, wherein 0 < a < 1,0 <b < 1,0 < a+b < 1,0 < x < 1,0 < y < 1,0 <
X+y < 1,1 < z < 1.5, M=Mn or Al；The ternary precursor includes ternary oxide presoma and ternary hydroxide forerunner
Body, the ternary hydroxide presoma are coated on ternary oxide presoma surface, point of the ternary oxide presoma
Minor are as follows: Ni1-x-yCoxMyOz, the molecular formula of the ternary hydroxide presoma is Ni1-a-bCoaMb(OH)2。
Further, preferably, the ternary oxide presoma is prepared using spray pyrolysis, the ternary
Hydroxide precursor is prepared using coprecipitation.Using ternary oxide presoma obtained by spray pyrolysis as crystal seed,
One layer of ternary hydroxide presoma is coated on ternary oxide presoma surface to get there are also compound heterogeneous using coprecipitation
The ternary precursor of structure.
As a total inventive concept, invention further provides bodies before a kind of ternary with composite heterogenous junction structure
The preparation method of body, includes the following steps:
S1 spray pyrolysis prepares ternary oxide presoma
Nickel salt, cobalt salt and manganese salt or the dissolution of aluminium salt solvent are configured to mixing salt solution A, the mixing salt solution A warp
After ultrasonic atomizatio, pyrolysis oven is loaded by carrier gas, pyrolysis obtains ternary oxide presoma, molecular formula Ni1-x-yCoxMyOz,
In 0 < x < 1,0 < y < 1,0 < x+y < 1,1 < z < 1.5, M=Mn or Al；
Molar ratio=1-x-y:x:y of Ni:Co:Mn (or Al) in the mixing salt solution A；
S2 prepares coprecipitation reaction crystal seed
The Ni that 1~3g S1 is prepared1-x-yCoxMyOzTernary oxide presoma is added to coprecipitation reaction bottom portion
As crystal seed, it is the ammonium hydroxide of 1~4mol/L as bottom liquid that 150~250ml concentration, which is then added, and being slowly stirred makes Ni1-x- yCoxMyOzPowder is evenly dispersed；
S3 prepares coprecipitation reaction molten metal
Nickel salt, cobalt salt and manganese salt or the dissolution of aluminium salt solvent are configured to mixing salt solution B, as co-precipitation molten metal
It is spare；Molar ratio=1-a-b:a:b of Ni:Co:Mn (or Al) in the mixing salt solution B, wherein 0 < a < 1,0 <b < 1,0 < a+b
< 1, M=Mn or Al；
S4 prepares coprecipitation reaction lye
The coprecipitation reaction lye is made of complexing agent and precipitating reagent by equal proportion mixing, the complexing agent be ammonium hydroxide or
The solution being configured to after ionized water or distilled water is added in ammonium salt, and the precipitating reagent is that water soluble alkali deionized water or distillation are water-soluble
The solution being configured to after solution；
The preparation of S5 coprecipitation reaction has the ternary precursor of composite heterogenous junction structure
The S3 molten metal prepared and the S4 lye prepared are pumped by S2 institute by peristaltic pump simultaneously under protective gas atmosphere
It states and carries out coprecipitation reaction in coprecipitation reaction kettle, adjusting coprecipitation reaction kettle rotating speed of agitator is coprecipitated to 300~800r/min
Shallow lake reaction temperature is 50~60 DEG C, and the addition speed of molten metal is 0.2~2ml/min, adjusts lye adding speed control pH and exists
10~12；Gained solidliquid mixture adopted after co-precipitation be washed with deionized after centrifugal filtration separates collect be placed in it is dry
Dry in dry case, obtained precipitation solid is the ternary precursor with composite heterogenous junction structure after drying, and molecular formula is
Ni1-a-bCoaMb(OH)2@Ni1-x-yCoxMyOz。
Further, preferably, the nickel salt is at least one in nickel chloride, nickel sulfate, nickel nitrate and nickel acetate
Kind, preferably nickel chloride；The cobalt salt is at least clock, preferably chlorination in cobalt chloride, cobaltous sulfate, cobalt nitrate and cobalt acetate
Cobalt；The manganese salt is at least one of manganese chloride, manganese sulfate, manganese nitrate and manganese acetate, preferably manganese chloride；The aluminium salt is
At least one of aluminium chloride, aluminum sulfate, aluminum nitrate and aluminum acetate, preferably aluminium chloride.
Further, preferably, total concentration of metal ions is 0.1~5mol/L in the mixing salt solution A；It is described
Total concentration of metal ions is 0.5~2mol/L in mixing salt solution B.
Further, preferably, carrier gas described in S1 is oxygen or air, preferably oxygen；The flow rate of carrier gas
For 2-6L/min；The pyrolysis oven is three sections of vertical temperature control furnaces, and the pyrolysis temperature is 650~900 DEG C.
Further, preferably, complexing agent concentration described in S4 is 1-4mol/L, and the complexing agent is preferably ammonia
Water；The precipitant concentration is 1-2mol/L；The water soluble alkali be LiOH, at least one of KOH and NaOH, preferably
NaOH。
Further, preferably, protective gas described in S5 is argon gas (Ar)；The drying box is forced air drying
Case, drying temperature are 60~100 DEG C, and drying time is 8~12h.
As a total inventive concept, the present invention further additionally provides a kind of tertiary cathode material, the tertiary cathode
Material is prepared into the ternary precursor with composite heterogenous junction structure described above or with preparation method described above
The ternary precursor with composite heterogenous junction structure arrived.The molecular formula of the tertiary cathode material is LiNi1-a-bCoaMbO2@
LiNi1-x-yCoxMyO2, wherein 0 < a < 1,0 <b < 1,0 < a+b < 1,0 < x < 1,0 < y < 1,0 < x+y < 1,1 < z < 1.5, M=Mn or Al.
As a total inventive concept, the present invention further provides a kind of preparation methods of tertiary cathode material, will be upper
State the described ternary precursor with composite heterogenous junction structure or by preparation method described above be prepared with compound
The ternary precursor and lithium salts mixed sintering of heterojunction structure are prepared up to tertiary cathode material.
Preferably, the lithium salts is LiOH, LiF and Li2CO3At least one of.
The invention has the following beneficial effects:
The present invention is combined using spray pyrolysis with coprecipitation, with ternary oxide presoma obtained by spray pyrolysis
Ni1-x-yCoxMyOz(M=Mn or Al) is crystal seed, using coprecipitation at one layer of ternary oxide presoma surface uniform deposition
Ternary hydroxide presoma Ni1-a-bCoaMb(OH)2(M=Mn or Al) is to get Ni1-a-bCoaMb(OH)2@Ni1-x-yCoxMyOz
(M=Mn or Al) has the ternary precursor of composite heterogenous junction structure；The present invention is further again with synthesized Ni1-a-bCoaMb
(OH)2@Ni1-x-yCoxMyOz(M=Mn or Al) compound heterogeneous presoma and lithium salts mixed sintering prepare LiNi1-a-bCoaMbO2@
LiNi1-x-yCoxMyO2(M=Mn or Al) tertiary cathode material.The tertiary cathode material boring structure that the present invention synthesizes,
Outside is fine and close shell, this special structure for solid spherical anode material prepared by traditional coprecipitation,
Material inherits the hollow structure in spray pyrolysis technologies, and thus activity is higher, and shortens lithium ion diffusion to a certain extent
Path guarantees that material has preferably circulating ratio performance.For the material prepared by spray pyrolysis merely, Ke Yibao
Card material still maintains spherical morphology during high temperature lithiumation, improves the tap density of material to a certain extent, thus
It ensure that material first charge discharge efficiency with higher and power density.Gradient ternary material can be prepared using this method simultaneously, dropped
Low nickelic positive electrode surface nickel content, improves storage and the chemical property of material.In addition, this method can also pass through regulation
In ternary precursor preparation process during spray pyrolysis precursor solution ingredient, the temperature and speed of spray pyrolysis are coprecipitated
The ingredient of the molten metal of shallow lake process, PH, the parameters such as temperature are to regulate and control the pattern, partial size and ingredient of tertiary cathode material.In short,
Tertiary cathode material using this method preparation has good layer structure, higher first charge discharge efficiency, height ratio capacity and excellent
Circulating ratio performance.
Detailed description of the invention
Fig. 1 is gained Ni in the embodiment of the present invention 10.8Co0.1Mn0.1(OH)2@Ni0.8Co0.1Mn0.1OxCompound heterogeneous presoma
SEM figure.
Fig. 2 is gained Ni in the embodiment of the present invention 10.8Co0.1Mn0.1(OH)2@Ni0.8Co0.1Mn0.1OxCompound heterogeneous presoma
The SEM of cross section schemes.
Fig. 3 is gained LiNi in the embodiment of the present invention 10.8Co0.1Mn0.1O2SEM figure.
Fig. 4 is gained LiNi in the embodiment of the present invention 10.8Co0.1Mn0.1O2The SEM of cross section schemes.
Fig. 5 is gained LiNi in the embodiment of the present invention 10.8Co0.1Mn0.1O2XRD diagram.
Fig. 6 is gained LiNi in the embodiment of the present invention 10.8Co0.1Mn0.1O2First charge-discharge curve graph.
Fig. 7 is gained LiNi in the embodiment of the present invention 10.8Co0.1Mn0.1O2Cycle performance figure.
Fig. 8 is gained LiNi in the embodiment of the present invention 10.8Co0.1Mn0.1O2High rate performance figure.
Fig. 9 is gained Ni in the embodiment of the present invention 20.85Co0.075Mn0.075(OH)2@Ni0.85Co0.075Mn0.075OxSEM
Figure.
Figure 10 is gained Li Ni in the embodiment of the present invention 20.85Co0.075Mn0.075O2SEM figure.
Figure 11 is gained LiNi in the embodiment of the present invention 20.85Co0.075Mn0.075O2First charge-discharge curve graph.
Figure 12 is gained LiNi in the embodiment of the present invention 20.85Co0.075Mn0.075O2Cycle performance figure.
Figure 13 is gained gained Ni in the embodiment of the present invention 30.5Co0.25Mn0.25(OH)2@Ni0.9Co0.05Mn0.05OxSEM
Figure.
Figure 14 is gained LiNi in the embodiment of the present invention 30.5Co0.25Mn0.25O2@LiNi0.9Co0.05Mn0.05O2SEM figure.
Figure 15 is gained gained Ni in the embodiment of the present invention 40.8Co0.15Al0.05(OH)2@Ni0.8Co0.15Al0.05OxSEM
Figure.
Figure 16 is gained LiNi in the embodiment of the present invention 40.8Co0.15Al0.05O2SEM figure.
Specific embodiment
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Except there is a special instruction, the various reagents used in the present invention, raw material be can commodity commercially or
Person can the product as made from well known method.
Embodiment 1:
A kind of LiNi with special construction0.8Co0.1Mn0.1O2Tertiary cathode material, preparation method include following step
It is rapid:
S1 spray pyrolysis prepares ternary oxide presoma
By NiCl2, CoCl2And MnCl2Being made into total concentration of metal ions according to the ratio (molar ratio) of 8:1:1 is 0.5mol/
The solution of L, solution are loaded into pyrolysis oven after ultrasonic atomizatio, by oxygen carrier gas, and the flow velocity of oxygen is 4L/min, hot at 750 DEG C
The Ni that solution obtains0.8Co0.1Mn0.1OxBeing collected by filtration through upper end nickel screen after presoma；
S2 prepares coprecipitation reaction crystal seed
By 2g Ni0.8Co0.1Mn0.1OxOxide precursor is added to coprecipitation reaction bottom portion as crystal seed；Configuration
The ammonium hydroxide 500ml of 3mol/L, taking 300mL is to pour into as bottom liquid in coprecipitation reaction kettle, and being slowly stirred makes
Ni0.8Co0.1Mn0.1OxPowder is evenly dispersed；
S3 prepares coprecipitation reaction molten metal
By NiCl2·6H2O、CoCl2·6H2O、MnCl2·4H2O's is configured to total metal ion by 8:1:1 (molar ratio)
Concentration is the mixed chloride aqueous solution of 0.5mol/L；
S4 prepares coprecipitation reaction lye
The NaOH solution that 100mL concentration is 1mol/L and the ammonium hydroxide that 100mL concentration is 3mol/L is taken to be uniformly mixed；
The preparation of S5 coprecipitation reaction has the ternary precursor of composite heterogenous junction structure
The S3 molten metal prepared and the S4 lye prepared are pumped by coprecipitation reaction by peristaltic pump simultaneously under an ar atmosphere
In kettle, rotating speed of agitator is 400r min-1, for the control of coprecipitation reaction temperature at 55 DEG C, the addition speed of molten metal is 0.5ml/
Min, adjusting lye adding speed makes pH control 11.3；Gained sediment is washed with deionized water through adopting after being co-precipitated by 2h
It washs to be collected after centrifugation twice and is placed in 80 DEG C of air dry ovens dry 8h, obtain Ni0.8Co0.1Mn0.1(OH)2@
Ni0.8Co0.1Mn0.1Ox.The object phase and pattern of gained oxide precursor are detected.
S6 prepares tertiary cathode material
By Ni0.8Co0.1Mn0.1(OH)2@Ni0.8Co0.1Mn0.1OxBe sintered at a temperature of 780 DEG C after lithium carbonate mixed grinding
15h, then to gained nickel-base anode material LiNi0.8Co0.1Mn0.1O2Object phase, pattern and electrochemistry can be carried out detection.
Fig. 1 is gained Ni in embodiment 10.8Co0.1Mn0.1(OH)2@Ni0.8Co0.1Mn0.1OxSEM spectrum, it can be seen that
Ni0.8Co0.1Mn0.1(OH)2Nanometer sheet depends on Ni0.8Co0.1Mn0.1OxMicrosphere surface homoepitaxial, most nanometer sheets are to hang down
It is directly grown in the direction of microsphere surface, and in criss-cross gesture arrangement, forms the compound heterogeneous presoma of " blooming on ball ".Figure
2 be gained Ni in embodiment 10.8Co0.1Mn0.1(OH)2@Ni0.8Co0.1Mn0.1OxCross section SEM spectrum, it can be seen that it is interior
Portion's disperse has the hollow structure of oxide nano particles.Fig. 3 is LiNi in the embodiment of the present invention 10.8Co0.1Mn0.1O2SEM figure
Spectrum, it can be seen that positive electrode inherits the spherical morphology of presoma well, and particle diameter distribution is uniform, and about 3~5 μm, table
One layer has been inlayed by Ni in face0.8Co0.1Mn0.1(OH)2The sintered fine and close primary particle of nanometer sheet lithiumation.Fig. 4 is implementation of the present invention
LiNi in example 10.8Co0.1Mn0.1O2Cross section SEM spectrum, the inside of particle is hollow structure.In addition, with compound heterogeneous forerunner
The internal structure of body is compared, and the hollow degree of synthesized positive electrode greatly reduces, this is because the lithium salts of melting penetrates into
Inside presoma, and and Ni0.8Co0.1Mn0.1(OH)2Nanometer sheet and Ni0.8Co0.1Mn0.1OxOne time lithiation occurs for nano particle
Caused by so that nanometer sheet/crystal grain grown up, be roughened.Fig. 5 is gained LiNi0.8Co0.1Mn0.1O2XRD spectrum, it is known that material have it is good
Good layer structure and low lithium nickel mixing degree.Fig. 6 is gained LiNi0.8Co0.1Mn0.1O2First charge-discharge curve, material
First discharge specific capacity and first charge-discharge efficiency are respectively 199.4mAhg under 0.1 multiplying power-1, 85.3%.Fig. 7 is gained
LiNi0.8Co0.1Mn0.1O2Cycle performance figure, material recycled 100 times under 1C multiplying power after specific discharge capacity and capacity keep
Rate is respectively 178.3mAhg-1, 97.5%.It is found that there is very excellent electricity using the tertiary cathode material that this method obtains
Chemical property.Fig. 8 is gained LiNi in embodiment 10.8Co0.1Mn0.1O2High rate performance figure, material in 0.1C, 0.5C, 1C,
Specific discharge capacity under 2C, 5C, 10C multiplying power is respectively 198.2mAhg-1, 185.0mAhg-1, 178.9mAhg-1,
173.3mAh·g-1, 161.9mAhg-1, 128.6mAhg-1, when current density turns again to 0.1C, specific discharge capacity is extensive
Again to 191.3mAhg-1, illustrate that the crystal structure of material is able to bear the quick deintercalation of lithium ion.
Embodiment 2:
A kind of LiNi with special construction0.85Co0.075Mn0.075O2Tertiary cathode material, preparation method include following
Step:
S1 spray pyrolysis prepares ternary oxide presoma
By NiCl2, CoCl2And MnCl2Being made into total concentration of metal ions according to the ratio (molar ratio) of 34:15:15 is
The solution of 0.5mol/L, solution are loaded into pyrolysis oven after ultrasonic atomizatio by oxygen, and the flow velocity of oxygen is 4L/min, at 780 DEG C
Under obtained Ni0.85Co0.075Mn0.075OxBeing collected by filtration through upper end nickel screen after presoma；
S2 prepares coprecipitation reaction crystal seed
By 1.8g Ni0.85Co0.075Mn0.075OxOxide precursor is added to coprecipitation reaction bottom portion as crystal seed；Match
The ammonium hydroxide 500ml for setting 3mol/L, taking 200mL is to pour into as bottom liquid in coprecipitation reaction kettle, and being slowly stirred makes
Ni0.85Co0.075Mn0.075OxPowder is evenly dispersed；
S3 prepares coprecipitation reaction molten metal
By NiCl2·6H2O、CoCl2·6H2O、MnCl2·4H2O by 34:15:15 (molar ratio) be configured to total metal from
Sub- concentration is the mixed chloride aqueous solution of 0.4mol/L；
S4 prepares coprecipitation reaction lye
The NaOH solution that 100mL concentration is 1mol/L and the ammonium hydroxide that 100mL concentration is 3mol/L is taken to be uniformly mixed；
The preparation of S5 coprecipitation reaction has the ternary precursor of composite heterogenous junction structure
It is anti-that the lye that the S3 metallic solution prepared and S4 are prepared is pumped by co-precipitation by peristaltic pump simultaneously under an ar atmosphere
It answers in kettle, rotating speed of agitator is 300r min-1, at 58 DEG C, the addition speed of molten metal is the control of coprecipitation reaction temperature
0.5ml/min, adjusting lye adding speed makes pH control 11.5；After 2h coprecipitation reaction by gained sediment spend from
Sub- water washing is collected after centrifugation twice is placed in 80 DEG C of air dry ovens dry 8h, obtains Ni0.85Co0.075Mn0.075(OH)2@
Ni0.85Co0.075Mn0.075Ox。
S6 prepares tertiary cathode material
By Ni0.85Co0.075Mn0.075(OH)2@Ni0.85Co0.075Mn0.075OxWith after lithium carbonate mixed grinding in 780 DEG C of temperature
Lower sintering 15h, then to gained LiNi0.85Co0.075Mn0.075O2Pattern and electrochemistry can be carried out detection.
Fig. 9 is Ni0.85Co0.075Mn0.075(OH)2@Ni0.85Co0.075Mn0.075OxSEM spectrum, it can be seen that
Ni0.85Co0.075Mn0.075(OH)2Nanometer sheet depends on Ni0.85Co0.075Mn0.075OxMicrosphere surface homoepitaxial, formation " are opened on ball
The compound heterogeneous presoma of flower ".Figure 10 is LiNi0.85Co0.075Mn0.075O2SEM spectrum, it can be seen that material is spherical morphology,
And particle diameter distribution is uniform, about 3~5 μm.Figure 11 is gained LiNi0.85Co0.075Mn0.075O2First charge-discharge curve, material
First discharge specific capacity and first charge-discharge efficiency are respectively 207.3mAhg under 0.1 multiplying power-1, 84.5%.Figure 12 is gained
LiNi0.85Co0.075Mn0.075O2Cycle performance figure, material recycled 100 times under 1C multiplying power after specific discharge capacity and capacity protect
Holdup is respectively 171.6mAhg-1, 92.3%.It is found that the LiNi obtained using this method0.85Co0.075Mn0.075O2Ternary is just
Pole material has very excellent cycle performance.
Embodiment 3:
A kind of tertiary cathode material LiNi with special construction0.5Co0.25Mn0.25O2@LiNi0.9Co0.05Mn0.05O2,
Preparation method the following steps are included:
S1 spray pyrolysis prepares ternary oxide presoma
By NiCl2·6H2O、CoCl2·6H2O、MnCl2·4H2O's is made into total gold by 18:1:1 (molar ratio) is soluble in water
Belong to the solution that ion concentration is 0.6mol/L, solution is loaded into pyrolysis oven after ultrasonic atomizatio, by oxygen, and the flow velocity of oxygen is 6L/
Min, the Ni being pyrolyzed at 750 DEG C0.9Co0.05Mn0.05OxBeing collected by filtration through upper end nickel screen after presoma；
S2 prepares coprecipitation reaction crystal seed
By 2g Ni0.9Co0.05Mn0.05OxOxide precursor is added to coprecipitation reaction bottom portion as crystal seed；Configuration
The ammonium hydroxide 500ml of 2mol/L, taking 300mL is to pour into as bottom liquid in coprecipitation reaction kettle, and being slowly stirred makes
Ni0.9Co0.05Mn0.05OxPowder is evenly dispersed；
S3 prepares coprecipitation reaction molten metal
By NiCl2·6H2O、CoCl2·6H2O、MnCl2·4H2O's is configured to total metal ion by 2:1:1 (molar ratio)
Concentration is the mixed chloride aqueous solution of 0.5mol/L；
S4 prepares coprecipitation reaction lye
The NaOH solution that 100mL concentration is 1mol/L and the ammonium hydroxide that 100mL concentration is 3mol/L is taken to be uniformly mixed；
The preparation of S5 coprecipitation reaction has the ternary precursor of composite heterogenous junction structure
Metallic solution and lye are pumped into coprecipitation reaction kettle simultaneously by peristaltic pump under an ar atmosphere, rotating speed of agitator
For 300r min-1, for the control of coprecipitation reaction temperature at 58 DEG C, the addition speed of molten metal is 0.4ml/min, adjusts lye addition
Speed makes pH control 11.4；Gained sediment is washed with deionized after 3h coprecipitation reaction and is received after being centrifuged twice
Collection is placed in 80 DEG C of air dry ovens dry 8h, obtains Ni0.5Co0.25Mn0.25(OH)2@Ni0.9Co0.05Mn0.05Ox；
S6 prepares tertiary cathode material
By Ni0.5Co0.25Mn0.25(OH)2@Ni0.9Co0.05Mn0.05OxWith burnt at a temperature of 780 DEG C after lithium carbonate mixed grinding
15h is tied, positive electrode LiNi is prepared0.5Co0.25Mn0.25O2@LiNi0.9Co0.05Mn0.05O2。
Figure 13 is Ni0.5Co0.25Mn0.25(OH)2@Ni0.9Co0.05Mn0.05OxSEM spectrum, it can be seen that
Ni0.5Co0.25Mn0.25(OH)2Nanometer sheet depends on Ni0.9Co0.05Mn0.05OxMicrosphere surface homoepitaxial is formed " blooming on ball "
Compound heterogeneous presoma.Figure 14 is LiNi0.5Co0.25Mn0.25O2@LiNi0.9Co0.05Mn0.05O2SEM spectrum, it can be seen that material
Material is spherical pattern, and particle diameter distribution is uniform, about 3~5 μm.
Embodiment 4:
A kind of LiNi with special construction0.8Co0.15Al0.05O2Tertiary cathode material, preparation method include following step
It is rapid:
S1 spray pyrolysis prepares ternary oxide presoma
By NiCl2, CoCl2And AlCl3Being made into total concentration of metal ions according to the ratio (molar ratio) of 16:3:1 is
The solution of 0.5mol/L, solution are loaded into pyrolysis oven after ultrasonic atomizatio, by oxygen, and the flow velocity of oxygen is 4L/min, at 750 DEG C
It is pyrolyzed obtained Ni0.8Co0.15Al0.05OxPresoma is collected by filtration through upper end nickel screen；
S2 prepares coprecipitation reaction crystal seed
By 2g Ni0.8Co0.15Al0.05OxOxide precursor is added to coprecipitation reaction bottom portion as crystal seed；Configuration
The ammonium hydroxide 500ml of 3mol/L, taking 200mL is to pour into as bottom liquid in coprecipitation reaction kettle, and being slowly stirred makes
Ni0.8Co0.15Al0.05OxPowder is evenly dispersed；
S3 prepares coprecipitation reaction molten metal
By NiCl2、CoCl2、AlCl3To be configured to total concentration of metal ions by 16:3:1 (molar ratio) be 0.4mol/L
Mixed chloride aqueous solution；
S4 prepares coprecipitation reaction lye
The NaOH solution that 100mL concentration is 1mol/L and the ammonium hydroxide that 100mL concentration is 3mol/L is taken to be uniformly mixed；
The preparation of S5 coprecipitation reaction has the ternary precursor of composite heterogenous junction structure
Metallic solution and lye are pumped into coprecipitation reaction kettle simultaneously by peristaltic pump under an ar atmosphere, rotating speed of agitator
For 400r min-1, for the control of coprecipitation reaction temperature at 58 DEG C, the addition speed of molten metal is 0.5ml/min, adjusts lye addition
Speed makes pH control 11.2；Gained sediment is washed with deionized after being co-precipitated and sets twice through being collected after centrifugation by 2h
In 8h dry in 80 DEG C of air dry ovens, Ni is obtained0.8Co0.15Al0.05(OH)2@Ni0.8Co0.15Al0.05Ox。
S6 prepares tertiary cathode material
By Ni0.8Co0.15Al0.05(OH)2@Ni0.8Co0.15Al0.05OxWith burnt at a temperature of 780 DEG C after lithium carbonate mixed grinding
15h is tied, LiNi is obtained0.8Co0.15Al0.05O2Positive electrode.
Figure 15 is Ni0.8Co0.15Al0.05(OH)2@Ni0.8Co0.15Al0.05OxSEM spectrum, it can be seen that
Ni0.8Co0.15Al0.05(OH)2Nanometer sheet depends on Ni0.8Co0.15Al0.05OxMicrosphere surface homoepitaxial is formed " blooming on ball "
Compound heterogeneous presoma.Figure 16 is LiNi0.8Co0.15Al0.05O2SEM spectrum, it can be seen that material be spherical pattern.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (8)
1. a kind of preparation method of the ternary precursor with composite heterogenous junction structure, which comprises the steps of:
S1 spray pyrolysis prepares ternary oxide presoma
Nickel salt, cobalt salt and manganese salt or the dissolution of aluminium salt solvent are configured to mixing salt solution A, the mixing salt solution A is through ultrasound
After atomization, pyrolysis oven is loaded by carrier gas, pyrolysis obtains ternary oxide presoma, molecular formula Ni1-x-yCoxMyOz, wherein 0 <
X < 1,0 < y < 1,0 < x+y < 1,1 < z < 1.5, M=Mn or Al；
Molar ratio=1-x-y:x:y of Ni:Co:Mn or Ni:Co:Al in the mixing salt solution A；
S2 prepares coprecipitation reaction crystal seed
The Ni that 1~3g S1 is prepared1-x-yCoxMyOzTernary oxide presoma is added to the portion's conduct of coprecipitation reaction bottom
Crystal seed, it is the ammonium hydroxide of 1~4mol/L as bottom liquid that 150~250ml concentration, which is then added, and being slowly stirred makes Ni1-x-yCoxMyOzPowder
End is evenly dispersed；
S3 prepares coprecipitation reaction molten metal
Nickel salt, cobalt salt and manganese salt or the dissolution of aluminium salt solvent are configured to mixing salt solution B, it is standby as co-precipitation molten metal
With；Molar ratio=1-a-b:a:b of Ni:Co:Mn or Ni:Co:Al in the mixing salt solution B, wherein 0 < a < 1,0 <b < 1,0 < a
+b<1；
S4 prepares coprecipitation reaction lye
The coprecipitation reaction lye is made of complexing agent and precipitating reagent by equal proportion mixing, and the complexing agent is ammonium hydroxide or ammonium salt
The solution being configured to after ionized water or distilled water is added, after the precipitating reagent is water soluble alkali deionized water or distilled water dissolution
The solution being configured to；
The preparation of S5 coprecipitation reaction has the ternary precursor of composite heterogenous junction structure
The lye that the S3 molten metal prepared and S4 are prepared is pumped into described in S2 altogether simultaneously by peristaltic pump under protective gas atmosphere
Coprecipitation reaction is carried out in precipitation reaction kettle, adjusts coprecipitation reaction kettle rotating speed of agitator to 300~800r/min, co-precipitation is anti-
Answering temperature is 50~60 DEG C, and the addition speed of molten metal is 0.2~2ml/min, adjust lye adding speed control pH 10~
12；Gained solidliquid mixture is adopted to be washed with deionized to collect after centrifugal filtration separates and is placed in by 2~4h after being co-precipitated
Dry in drying box, obtained precipitation solid is the ternary precursor with composite heterogenous junction structure after drying, and molecular formula is
Ni1-a-bCoaMb(OH)2@Ni1-x-yCoxMyOz。
2. the preparation method of ternary precursor according to claim 1, it is characterised in that: the nickel salt is nickel chloride, sulphur
At least one of sour nickel, nickel nitrate and nickel acetate；The cobalt salt be cobalt chloride, cobaltous sulfate, cobalt nitrate and cobalt acetate in extremely
A few clock；The manganese salt is at least one of manganese chloride, manganese sulfate, manganese nitrate and manganese acetate；The aluminium salt is aluminium chloride, sulphur
At least one of sour aluminium, aluminum nitrate and aluminum acetate.
3. the preparation method of ternary precursor according to claim 1, it is characterised in that: total in the mixing salt solution A
Concentration of metal ions is 0.1~5mol/L；Total concentration of metal ions is 0.5~2mol/L in the mixing salt solution B.
4. the preparation method of ternary precursor according to claim 1, it is characterised in that: carrier gas described in S1 be oxygen or
Air；The flow rate of carrier gas is 2-6L/min；The pyrolysis temperature is 650~900 DEG C.
5. the preparation method of ternary precursor according to claim 1, it is characterised in that: complexing agent concentration described in S4 is
1-4mol/L；The precipitant concentration is 1-2mol/L；The water soluble alkali is LiOH, at least one of KOH and NaOH.
6. a kind of tertiary cathode material, it is characterised in that: have the described in any item preparation methods of claim 1-5 to be prepared
The ternary precursor with composite heterogenous junction structure.
7. a kind of preparation method of tertiary cathode material, it is characterised in that: by the described in any item preparation methods of claim 1-5
The ternary precursor with composite heterogenous junction structure being prepared is prepared with lithium salts mixed sintering up to tertiary cathode material.
8. the preparation method of tertiary cathode material according to claim 7, it is characterised in that: the lithium salts is LiOH, LiF
And Li2CO3At least one of.
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