CN109860561A - A kind of tiny balloon and its preparation method and application of richness lithium manganese boron - Google Patents
A kind of tiny balloon and its preparation method and application of richness lithium manganese boron Download PDFInfo
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Abstract
The present invention provides a kind of tiny balloons and its preparation method and application of rich lithium manganese boron.The preparation method includes: to be dispersed in water Ni-Co-B alloy microballoon, and manganese source and precipitating reagent is added, and adjusts pH, carries out hydro-thermal reaction, obtains MnCO3@Ni-Co-B presoma；By MnCO3@Ni-Co-B presoma is mixed with lithium source, sublevel section calcining, obtains the tiny balloon of rich lithium manganese boron.Tiny balloon of the invention can be used as positive electrode, have higher capacity, compared with high rate capability and preferable cyclical stability.
Description
Technical field
The present invention relates to a kind of tiny balloon more particularly to a kind of preparation methods of the tiny balloon of rich lithium manganese boron, belong to
Technical field of material.
Background technique
Lithium-rich manganese base material is a kind of layered oxide positive electrode, has class α-NaFeO2Layer structure, belong to six
The R of prismatic crystal system3-mSpace group, having is more than the specific capacity of 250mAh/g and the high working voltage of > 4.3V, and height ratio capacity makes
The material has broad application prospects in fields such as electric automobiles.
In lithium-rich manganese base material, although rich lithium material has high-energy density, high rate performance is bad, in cyclic process
Interface side reaction and structure transformation easily occurs, leads to the rapid decaying of battery capacity.The modification of this problem is mainly adopted at present
Doping and surface coated method are taken, but does not play improvement substantially.
Summary of the invention
In order to solve the above-mentioned technical problem, the purpose of the present invention is to provide a kind of with higher capacity, forthright compared with high power
The positive electrode of energy, preferable cyclical stability and long-life.
It in order to achieve the above technical purposes, should the present invention provides a kind of preparation method of the tiny balloon of rich lithium manganese boron
Preparation method the following steps are included:
Ni-Co-B alloy microballoon is dispersed in 30mL-80mL water, the manganese source of 2mmol-20mmol and suitable is added
Precipitating reagent adjusts pH to 3-7, and hydro-thermal reaction 4h-12h, obtains MnCO at 120 DEG C -180 DEG C3@Ni-Co-B presoma；
By MnCO3@Ni-Co-B presoma is mixed with lithium source, calcines 2h-8h at air atmosphere, 400 DEG C -500 DEG C, so
5h-20h is calcined at 750 DEG C -900 DEG C afterwards, obtains the tiny balloon xLi of rich lithium manganese boron2MnO3·(1-x)
LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)y。
In a specific embodiment of the invention, the tiny balloon xLi of obtained rich lithium manganese boron2MnO3·(1-x)
LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)yIn x be 0.2-0.8, y=1,1.03,1.05,1.07,1.09 or 1.12.
Preparation method of the invention realizes the gradient distribution of surface richness manganese, internal rich nickel using Kinkendal Effect, obtains
To xLi2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)yHollow microsphere structure.
Wherein, rich manganese can use Mn on surface4+Structural stability protection electrochemical reaction process in charge-exchange
Region reduces Ion transfer impedance.Internal core richness Ni2+The Spinel that can effectively improve in charge and discharge process generates,
The coulombic efficiency and capacity for improving material play.In addition, boron can increase substantially the ionic conductivity of inner layer material, make sky
Particle inside heart microballoon can also play higher performance.
In addition, the preparation method can regulate and control the gradient distribution of manganese and nickel, make work by calcination temperature and soaking time
The modulation of skill parameter is easier, controllability is stronger.
In the preparation process in accordance with the present invention, Kinkendal Effect (kirkendall effect) is metal in solid matter
A kind of diffusion phenomena that ion occurs.Since presoma kernel is Ni-Co-B alloy microballoon, surface is wrapped in the outer of Fu Meng
Layer, forms the concentration difference and charge differences of metallic element, due to a Ni2+It will be with a Mn4+In conjunction with just can guarantee+3
Valence state, therefore concentration difference and charge difference drive that Mn is mobile to kernel and Ni, Co and B element outer layers are mobile, are moved by ion
Move the hollow microsphere structure for forming gradient distribution.
In a specific embodiment of the invention, Ni-Co-B alloy microballoon is prepared according to the following steps to obtain:
Nickel source, cobalt source are added in sodium hydroxide solution, stabilizer is added, 0.5h is stirred, obtains metal hydroxides
Colloidal sol；Wherein, nickel source, the molar ratio of cobalt source are 1:1；The nickel source of every 1-5mmol is added in the sodium hydroxide solution of 100mL；
Under conditions of metal hydroxides colloidal sol is placed in ultrasound, stirring, the water-soluble of the boron hydride of 10mL is instilled dropwise
Liquid obtains black precipitate, by black precipitate washing, filtering, drying, obtains Ni-Co-B alloy microballoon.
In the preparation process in accordance with the present invention, Ni, Co and B element are equably precipitated by the method for chemical plating, is protected
Being uniformly distributed for B element doping is demonstrate,proved.
In a specific embodiment of the invention, the preparation method of the tiny balloon of rich lithium manganese boron may include:
Step 1: nickel source, cobalt source are added in sodium hydroxide solution, and stabilizer is added, and stirring obtains metal hydrogen-oxygen
Compound colloidal sol；Wherein, nickel source, the molar ratio of cobalt source are 1:1；The nickel source of every 1mmol-5mmol is added to the hydroxide of 100mL
In sodium solution.
In step 1, the nickel source used is nickel sulfate [NiSO4], nickel acetate [Ni (Ac)2], nickel nitrate [Ni (NO3)2]
One or more of combination.
In step 1, the cobalt source used is cobaltous sulfate [CoSO4], cobalt acetate [Co (Ac)2], cobalt nitrate [Co (NO3)2]
One or more of combination.
In step 1, the mass concentration of the sodium hydroxide solution used is 0.02M-0.2M.For example, the hydrogen-oxygen used
The mass concentration for changing sodium solution can be 0.05M, 0.08M, 0.1M, 0.15M, 0.18M.
In step 1, the purpose for adding stabilizer is stable sol system.The stabilizer used can be polyethylene glycol
(PEG), the combination of one or more of lactic acid, ammonium citrate.
In step 1, stabilizer 0.1g-0.5g is added in the sodium hydroxide solution of every 100mL.
In step 1, the time of stirring can be 0.5h.
In a specific embodiment of the invention, the preparation method of the tiny balloon of rich lithium manganese boron may include:
Step 2: metal hydroxides colloidal sol is placed in ultrasonic, stirring strong decentralized environment, instills 10mL's dropwise
The aqueous solution of boron hydride, obtains black precipitate, by black precipitate washing, filtering, drying, obtains Ni-Co-B alloy microballoon.
In step 2, the lower aqueous solution that boron hydride is added, can make boron in ultrasound and the strong decentralized environment of stirring
The aqueous solution (reducing agent) of hydride is contacted with more sticky metal hydroxides colloidal sol more dispersedly, keeps reaction more equal
It is even.
In step 2, ultrasonic power can be 20-100W.
In step 2, the speed of stirring can be 300r/min-1200r/min.
In step 2, instillation speed is 1 drop/1s-1 drop/15s.
In step 2, the aqueous solution of boron hydride is that boron hydride is incorporated in water, and stirring 0.5h is formed.Its
In, the concentration of the aqueous solution of boron hydride can be 0.01mol/L-0.1mol/L.
In step 2, boron hydride can be lithium borohydride (LiBH4), sodium borohydride (NaBH4), potassium borohydride
(KBH4) one or more of combination.
The uniform Ni-Co-B of boron (B) Elemental redistribution is prepared by step 1 and step 2 in preparation method of the invention
Alloy microballoon, hard template of the alloy microballoon as subsequent synthesis tiny balloon, has the tiny balloon being prepared hollow
Structure and rich lithium ternary (Ni-Co-Mn) material for thering is borate to adulterate.
The present invention makes B element and Ni, Co just be uniformly mixed to form alloying in atom level by step 1 and step 2
Microballoon, as depicted in figs. 1 and 2, the doping of the borate of atom level can increase substantially cyclical stability and the raising of material
Electro-chemical activity.B, Ni, Co are evenly dispersed in atom level it can be seen from the EDX-mapping of Fig. 1, illustrate presoma
It is uniformly mixed in middle various elements microscopic ranges.
In a specific embodiment of the invention, the preparation method of the tiny balloon of rich lithium manganese boron may include:
Step 3: Ni-Co-B alloy microballoon is dispersed in 30mL-80mL water, be added 2mmol-20mmol manganese source and
Suitable precipitating reagent, after adjusting pH to 3-7, hydro-thermal reaction 4h-12h, obtains MnCO at 120 DEG C -180 DEG C3Before@Ni-Co-B
Drive body.
In step 3, the manganese source used can be manganese sulfate [MnSO4], manganese acetate [Mn (Ac)2], manganese nitrate [Mn
(NO3)2] one or more of combination.
In step 3, precipitating reagent makes manganese element precipitate to form rich manganese outer layer in Ni-Co-B alloy microsphere surface.Wherein,
The additive amount of precipitating reagent is 1 times -5 times of the quality of manganese source.
In step 3, the precipitating reagent used can be urea and/or melamine.
In a specific embodiment of the invention, the preparation method of the tiny balloon of rich lithium manganese boron may include:
Step 4: by MnCO3@Ni-Co-B presoma is mixed with lithium source, is calcined at air atmosphere, 400 DEG C -500 DEG C
Then 2h-8h calcines 5h-20h at 750 DEG C -900 DEG C, obtain the tiny balloon xLi of rich lithium manganese boron2MnO3·(1-x)
LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)y。
In step 4, the too fast rupture for causing spherical structure of heating rate can be prevented by calcine by steps.
In step 4, after mixing with lithium source, classification calcining is carried out, forms Mn element in table using Kinkendal Effect
The tiny balloon of layer enrichment and distribution gradient.As shown in the EDX-mapping of Fig. 3, core of the Ni and Mn element in spheric granules
Heart content is lower, this is because ball is hollow structure；Ni element is more in the enrichment of the inside of shell, and Mn element is hollow micro-
The surface enrichment of spherical shell layer, two kinds of element distribution gradients in thickness dimension.
In step 4, the lithium source used can be lithium hydroxide (LiOH), lithium carbonate (Li2CO3), lithium nitrate (LiNO3)
One or more of combination.
In step 4, the additive amount of lithium source is added on the basis of the total amount of manganese metal, cobalt and nickel.Wherein, Mn+Co
+ Ni) molar ratio of summation and Li is 1:y (1+0.33x).
The present invention also provides a kind of xLi2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)yIt is hollow micro-
Ball, wherein x 0.2-0.8, y=1,1.03,1.05,1.07,1.09 or 1.12, which is through the invention
What the preparation method of the tiny balloon of above-mentioned richness lithium manganese boron was prepared.
XLi of the invention2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)yThe granularity of tiny balloon is 2
μm -40 μm, hollow shell layer with a thickness of 2 μm -20 μm.
The granularity of the tiny balloon and the thickness of hollow shell layer can be biased to according to the demand of power and energy density, pass through tune
Section technological parameter is controlled.
Invention further provides a kind of positive electrode, which is by above-mentioned xLi of the invention2MnO3·(1-x)
LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)yMade of tiny balloon.
Positive electrode of the invention can be used as the anode of battery, and battery here includes but is not limited to lithium ion battery.
It is micro- that the method that preparation method of the invention passes through chemical plating first obtains the Ni-Co-B alloy that B element is evenly distributed
Ball, and synthesize using the alloy microballoon as hard template the tiny balloon of rich lithium manganese boron.The method of chemical plating makes B element and Ni, Co
In atom level just uniformly mixing, alloy microballoon is formed, the circulation that the doping of atom level borate can increase substantially material is steady
It is qualitative and improve electro-chemical activity.
Preparation method of the invention forms Mn element in surface layer enrichment and the sky of distribution gradient using Kinkendal Effect
Bulbus cordis structure guarantees good electrochemical reaction interface using the high stability of manganese element, and hollow configuration can obtain
More electrochemical reaction active sites, keep the capacity of material higher.
The simple process of preparation method of the invention, stability is preferable, and technological parameter is easy to regulate and control.
The xLi that preparation method through the invention obtains2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)y
Tiny balloon, under 2-4.8V voltage window, 0.2C multiplying power, specific discharge capacity reaches 262mAh/g or more, and 50 times circulation is held
Measuring conservation rate is 91% or more.
Detailed description of the invention
Fig. 1 is the EDX-Mapping figure of the alloy microballoon in the embodiment of the invention.
Fig. 2 is the SEM image of the alloy microballoon in the embodiment of the invention.
Fig. 3 is the EDX-Mapping figure of the tiny balloon in the embodiment of the invention.
Fig. 4 is the 0.5Li of embodiment 12MnO3·0.5LiNi0.33Co0.33Mn0.33O1.95·(BO3)0.03Tiny balloon is swept
Retouch electron microscope.
Fig. 5 is the cycle performance figure of the positive electrode 0.2C multiplying power of embodiment 1.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
Present embodiments provide 0.5Li2MnO3·0.5LiNi0.33Co0.33Mn0.33O1.95·(BO3)0.03Tiny balloon,
Through the following steps that be prepared.
Step 1: the NiSO of 3mmol is weighed4With the Co (Ac) of 3mmol2, it is molten for the NaOH of 0.05M that 100mL, concentration is added
The PEG of 0.3g is added in liquid, forms stable colloidal sol after stirring 0.5h.
Step 2: the KBH of 0.6mmol is weighed4, with magnetic agitation 0.5h after 15mL deionized water dissolving, formation is stablized molten
Liquid.
Step 3: by the colloidal sol of step 1 be put into 100w ultrasound, 500r/min stirring environment in, with 1 drop/3s speed
Degree instills the KBH of step 2 dropwise4Solution reacts 30min, obtains black precipitate, and after washing of precipitate filters, drying obtains Ni-
Co-B alloy microballoon.
Step 4: it by the Ni-Co-B alloy microballoon ultrasonic disperse of step 3 in the deionized water of 80mL, is added
The MnSO of 12mmol4With 6g urea, is adjusted after pH is 6.5 and be transferred in the water heating kettle of 100mL with ammonium hydroxide, reacted at 125 DEG C
6h obtains MnCO3@Ni-Co-B presoma.
Step 5: presoma and LiOH being mixed with the molar ratio of 1:1.05, calcine 5h at air atmosphere, 450 DEG C,
Then 12h is calcined at 800 DEG C, obtains 0.5Li2MnO3·0.5LiNi0.33Co0.33Mn0.33O1.95·(BO3)0.03Tiny balloon.
Its structure is as shown in Figure 4.
The above-mentioned tiny balloon of the present embodiment first discharge specific capacity under the electrochemical window of 2-4.8V, 0.2C multiplying power
For 262mAh/g, 50 cyclic specific capacity conservation rates are 91%, as shown in Figure 5.
Embodiment 2
Present embodiments provide a kind of 0.4Li2MnO3·0.6LiNi0.33Co0.33Mn0.33O1.97·(BO3)0.02It is hollow micro-
Ball, through the following steps that be prepared.
Step 1: the Ni (Ac) of 1mmol is weighed2With the CoSO of 1mmol4, it is molten for the NaOH of 0.2M that 100mL, concentration is added
The lactic acid of 0.5g is added in liquid, forms stable colloidal sol after stirring 0.5h.
Step 2: the LiBH of 0.1mmol is weighed4, with magnetic agitation 0.5h after 10mL deionized water dissolving, formed and stablized
Solution.
Step 3: by the colloidal sol in step 1 be put into 20w ultrasound, 1200r/min stirring environment in, dropwise instill step
KBH in rapid two4Solution, reaction obtain black precipitate, and after black precipitate washing filters, it is micro- that drying obtains Ni-Co-B alloy
Ball.
Step 4: by the Ni-Co-B alloy microballoon ultrasonic disperse of step 3 in 30mL deionized water, it is added 3mmol's
MnSO4With 1g urea, is adjusted after pH is 3 and be transferred in the water heating kettle of 100mL with ammonium hydroxide, reacted 12h at 180 DEG C, obtain
MnCO3@Ni-Co-B presoma.
Step 5: by presoma and LiNO3It is mixed with the molar ratio of 1:1.09, calcines 2h at air atmosphere, 500 DEG C,
Then 5h is calcined at 900 DEG C, obtains 0.4Li2MnO3·0.6LiNi0.33Co0.33Mn0.33O1.97·(BO3)0.02Tiny balloon.
The above-mentioned tiny balloon of the present embodiment first discharge specific capacity under the electrochemical window of 2-4.8V, 0.2C multiplying power
For 255mAh/g, 50 cyclic specific capacity conservation rates are 82%.
Embodiment 3
Present embodiments provide a kind of 0.25Li2MnO3·0.75LiNi0.33Co0.33Mn0.33O1.925·(BO3)0.05It is hollow
Microballoon, through the following steps that be prepared.
Step 1: the NiSO of 5mmol is weighed4With the Co (NO) of 5mmol3, it is molten for the NaOH of 0.2M that 100mL, concentration is added
0.1g ammonium citrate is added in liquid, forms stable colloidal sol after stirring 0.5h.
Step 2: the NaBH of 1mmol is weighed4, with magnetic agitation 0.5h after 30mL deionized water dissolving, formation is stablized molten
Liquid.
Step 3: by the colloidal sol of step 1 be put into 50w ultrasound, 300r/min stirring environment in, instill step 2 dropwise
KBH4Solution, reaction obtain black precipitate, and after black precipitate washing filters, drying obtains Ni-Co-B alloy microballoon.
Step 4: by the Ni-Co-B alloy microballoon ultrasonic disperse of step 3 in 50mL deionized water, 10mmol is added
MnSO4With 5g melamine, is adjusted after pH is 7 and is transferred in the water heating kettle of 100mL with ammonium hydroxide, react 6h at 180 DEG C,
Obtain MnCO3@Ni-Co-B presoma.
Step 5: by presoma and Li2CO3It is mixed with the molar ratio of 1:0.535, is calcined at air atmosphere, 400 DEG C
Then 8h calcines 20h at 750 DEG C, obtains 0.25Li2MnO3·0.75LiNi0.33Co0.33Mn0.33O1.925·(BO3)0.05It is empty
Heart microballoon.
The above-mentioned tiny balloon of the present embodiment first discharge specific capacity under the electrochemical window of 2-4.8V, 0.2C multiplying power
For 234mAh/g, 50 cyclic specific capacity conservation rates are 88.5%.
Embodiment 4
Present embodiments provide 0.6Li2MnO3·0.4LiNi0.33Co0.33Mn0.33O1.96·(BO3)0.04Tiny balloon,
Through the following steps that be prepared.
Step 1: the NiSO of 3mmol is weighed4With the Co (NO) of 3mmol3, it is molten for the NaOH of 0.16M that 100mL, concentration is added
Liquid is added stabilizer (lactic acid of the PEG and 0.1g of 0.1g), forms stable colloidal sol after stirring 0.5h.
Step 2: the LiBH of 0.9mmol is weighed4, with magnetic agitation 0.5h after 20mL deionized water dissolving, formed and stablized
Solution.
Step 3: by the colloidal sol of step 1 be put into 70w ultrasound, 800r/min stirring environment in, instill step 2 dropwise
NaBH4Solution, reaction obtains black precipitate, and after washing filters, drying obtains Ni-Co-B alloy microballoon.
Step 4: it by the Ni-Co-B alloy microballoon ultrasonic disperse of step 3 in 60mL deionized water, is added
16.5mmol MnSO4, 2g urea and 3g melamine, adjusted after pH is 4.5 and be transferred in the water heating kettle of 100mL with ammonium hydroxide,
7h is reacted at 150 DEG C, obtains MnCO3@Ni-Co-B presoma.
Step 5: by presoma and LiNO3It is mixed with the molar ratio of 1:1.12, calcines 6h at air atmosphere, 420 DEG C,
Then 15h is calcined at 800 DEG C, obtains 0.6Li2MnO3·0.4LiNi0.33Co0.33Mn0.33O1.96·(BO3)0.04Tiny balloon.
The above-mentioned tiny balloon of the present embodiment first discharge specific capacity under the electrochemical window of 2-4.8V, 0.2C multiplying power
For 270mAh/g, 50 cyclic specific capacity conservation rates are 79.5%.
Embodiment 5
Present embodiments provide 0.1Li2MnO3·0.9LiNi0.33Co0.33Mn0.33O1.98·(BO3)0.015Tiny balloon,
Through the following steps that be prepared.
Step 1: the NiSO of 4mmol is weighed4With the Co (NO) of 4mmol3, it is molten for the NaOH of 0.2M that 100mL, concentration is added
Liquid is added stabilizer (0.2g lactic acid and 0.2g ammonium citrate), forms stable colloidal sol after stirring 0.5h.
Step 2: the NaBH of 0.2mmol is weighed4, with magnetic agitation 0.5h after 15mL deionized water dissolving, formed and stablized
Solution.
Step 3: by the colloidal sol of step 1 be put into 45w ultrasound, 350r/min strong mixing environment in, instill step dropwise
Two NaBH4Solution, reaction obtains black precipitate, and after washing filters, drying obtains Ni-Co-B alloy microballoon.
Step 4: by the Ni-Co-B alloy microballoon ultrasonic disperse of step 3 in 40mL deionized water, 5.3mmol is added
MnSO4, 1g urea and 1g melamine, adjusted after pH is 3.5 and be transferred in the water heating kettle of 100mL with ammonium hydroxide, at 160 DEG C
Lower reaction 6h, obtains MnCO3@Ni-Co-B presoma.
Step 5: presoma and LiOH being mixed with the molar ratio of 1:1.09, calcine 5h at air atmosphere, 460 DEG C,
Then 16h is calcined at 780 DEG C, obtains 0.1Li2MnO3·0.9LiNi0.33Co0.33Mn0.33O1.98·(BO3)0.015It is hollow micro-
Ball.
The above-mentioned tiny balloon of the present embodiment first discharge specific capacity under the electrochemical window of 2-4.8V, 0.2C multiplying power
For 255mAh/g, 50 cyclic specific capacity conservation rates are 86.8%.
Claims (10)
1. a kind of preparation method of the tiny balloon of richness lithium manganese boron, which is characterized in that the preparation method the following steps are included:
Ni-Co-B alloy microballoon is dispersed in 30mL-80mL water, the manganese source and suitable precipitating of 2mmol-20mmol is added
Agent adjusts pH to 3-7, and hydro-thermal reaction 4h-12h, obtains MnCO at 120 DEG C -180 DEG C3@Ni-Co-B presoma；
By the MnCO3@Ni-Co-B presoma is mixed with lithium source, calcines 2h-8h at air atmosphere, 400 DEG C -500 DEG C, then
5h-20h is calcined at 750 DEG C -900 DEG C, obtains the tiny balloon xLi of rich lithium manganese boron2MnO3·(1-x)
LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)y。
2. preparation method according to claim 1, which is characterized in that the tiny balloon xLi of the richness lithium manganese boron2MnO3·(1-
x)LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)yMiddle x is 0.2-0.8, y=1,1.03,1.05,1.07,1.09 or 1.12.
3. preparation method according to claim 1, which is characterized in that the Ni-Co-B alloy microballoon is according to following step
Suddenly it is prepared:
Nickel source, cobalt source are added in sodium hydroxide solution, stabilizer is added, stirring obtains metal hydroxides colloidal sol；Its
In, the nickel source, the molar ratio of cobalt source are 1:1；The nickel source of every 1mmol-5mmol is added in the sodium hydroxide solution of 100mL；
Under conditions of the metal hydroxides colloidal sol is placed in ultrasound, stirring, the water-soluble of the boron hydride of 10mL is instilled dropwise
Liquid obtains black precipitate, by black precipitate washing, filtering, drying, obtains Ni-Co-B alloy microballoon.
4. preparation method according to claim 3, which is characterized in that the nickel source is nickel sulfate, in nickel acetate, nickel nitrate
A combination of one or more；
The mass concentration of the sodium hydroxide solution is 0.02M-0.2M；
Preferably, the cobalt source is the combination of one or more of cobaltous sulfate, cobalt acetate, cobalt nitrate；
Preferably, the concentration of the aqueous solution of the boron hydride is 0.01mol/L-0.1mol/L；
Preferably, the boron hydride that the aqueous solution of the boron hydride uses is in lithium borohydride, sodium borohydride, potassium borohydride
A combination of one or more.
5. preparation method according to claim 3, which is characterized in that the power of the ultrasound is 20W-100W；
Preferably, the speed of the stirring is 300r/min-1200r/min；
Preferably, the instillation speed of the aqueous solution of the boron hydride is 1 drop/1s-1 drop/15s.
6. preparation method according to claim 3, which is characterized in that the stabilizer is polyethylene glycol, lactic acid, citric acid
The combination of one or more of ammonium；
Preferably, stabilizer 0.1g-0.5g is added in the sodium hydroxide solution of every 100mL；
Preferably, the manganese source is the combination of one or more of manganese sulfate, manganese acetate, manganese nitrate；
Preferably, the precipitating reagent is urea and/or melamine；
It is highly preferred that the additive amount of the precipitating reagent is 1 times -5 times of the quality of manganese source.
7. preparation method according to claim 1, which is characterized in that the lithium source is lithium hydroxide, lithium carbonate, lithium nitrate
One or more of combination；
Preferably, the molar ratio of (Mn+Co+Ni) and Li are 1:y (1+0.33x).
8. a kind of xLi2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)yTiny balloon, which is characterized in that the sky
Heart microballoon is prepared by the preparation method of the tiny balloon of the described in any item rich lithium manganese boron of claim 1-7,
In, x 0.2-0.8, y=1,1.03,1.05,1.07,1.09 or 1.12.
9. tiny balloon according to claim 8, which is characterized in that the granularity of the tiny balloon is 2 μm -40 μm, hollow
Shell with a thickness of 2 μm -20 μm.
10. a kind of positive electrode, which is characterized in that the positive electrode is the xLi as described in claim 8 or 92MnO3·(1-x)
LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)yMade of tiny balloon.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910112283.1A CN109860561B (en) | 2019-02-13 | 2019-02-13 | Lithium-manganese-boron-rich hollow microsphere and preparation method and application thereof |
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| CN201910112283.1A CN109860561B (en) | 2019-02-13 | 2019-02-13 | Lithium-manganese-boron-rich hollow microsphere and preparation method and application thereof |
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| CN114220667A (en) * | 2021-12-31 | 2022-03-22 | 福州大学 | Hollow nickel hydroxide needle-punched microsphere electrode material and preparation method and application thereof |
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