CN109713250A - A kind of preparation method of the core-shell structure presoma of anode material of lithium battery - Google Patents
A kind of preparation method of the core-shell structure presoma of anode material of lithium battery Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of the core-shell structure presoma of anode material of lithium battery, belong to electrode material of lithium battery field, using saturated solution deposition method, by conventional precursor preparation at the presoma with core-shell structure.The preparation method that the present invention uses is low for equipment requirements, and operating method is simple, and the core-shell structure presoma of preparation has the shell of uniform, controllable.At 4.50V and higher voltage, compared with the positive electrode of conventional precursor preparation, the positive electrode of core-shell structure precursor preparation has better cycle performance.
Description
Technical field
The invention belongs to electrode material of lithium battery fields, are related to a kind of core-shell structure presoma of anode material of lithium battery
Preparation method.
Background technique
The anode material of lithium battery of layer structure is current the most abundant, the most widely used consumer lithium-ion electric of research
Pond positive electrode, such as LiCoO2、LiNi0.5Co0.2Mn0.3O2.In recent years, the operating voltage of consumer lithium battery is higher and higher, right
The requirements such as mass energy density, the security performance of positive electrode are also higher and higher.Core is the core-shell structure anode of layer structure
Material, core can guarantee that mass energy density, casing part have better high-temperature stability, can expire simultaneously
Sufficient high-energy density and high safety performance.
This kind of positive electrode is applied in lithium ion battery product more and more widely.For example, Jens Martin
The patent (US20120134914A1) of Paulsen passes through dry mixed LiCoO2、Li2CO3, Ni/MnOOH prepares
LiNi0.5Mn0.5O2The stratiform LiCoO of island cladding2；The patent (WO2009057834A1) of King Seong-Bae is mixed with dry method
The mode of conjunction prepares the Core-shell structure material of olivine structural cladding layer structure；But both methods cannot be guaranteed shell point
Cloth is uniform.It is described in the patent (EP2973794B1) of HAO Jianjun and first prepares Shell Materials with the precipitation method, then with wet
Shell Materials are coated on stratiform LiCo by method cladding0.2Ni0.8O2On surface, the shell that the precipitation method are prepared is evenly distributed, but this
Kind complex process.The above several method is the common method for preparing Core-shell structure material.In addition, the patent of SUN Yang Kook
(EP2102927B1) core-shell structure presoma is prepared with coprecipitation, then prepares LiMn1-xMxOyCore-shell material.This side
Method provides focusing on for technique on qualified core-shell structure presoma, and the coprecipitation process of use is complicated.
The above method has shell to be unevenly distributed or the problem of complex process.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of the core-shell structure presoma of anode material of lithium battery.Using
Saturated solution deposition method prepares the presoma of core-shell structure, this method can make the metal salt in solution one it is longer plus
During thermal agitation, it is gradually precipitated and is coated on conventional presoma surface, forms uniform shell.Nucleocapsid knot prepared by the present invention
Structure presoma has equally distributed shell, and preparation process is simple.The lithium battery anode that this core-shell structure precursor preparation goes out
Material capacity with higher and good security performance under the even higher voltage of 4.5V.
A kind of preparation method of the core-shell structure presoma of anode material of lithium battery, step include:
Metal salt and solvent are weighed, it is molten to be configured to metal salt for metallic element needed for which contains shell to be prepared
Liquid；
The conventional presoma being made of at least one of cobaltosic oxide, nickel cobalt manganese hydroxide is weighed, is slowly added to
Into above-mentioned metal salt solution, heating stirring obtains mixture until solvent volatilizees completely to solution supersaturation；
Said mixture is put into standing and drying in baking oven, after being completely dried, upper one layer of the cladding on conventional presoma surface
Uniform shell is to get arriving core-shell structure presoma.
Further, the concentration of metallic element is greater than 0 in the metal salt solution, is less than or equal to its saturated concentration.
Further, the volume of the metal salt solution is calculated by following formula:
V=W × m × 10-6/ρ (1)
Wherein, V is the volume (unit is mL) of metal salt solution, and W is the quality (unit is g) of conventional presoma, and m is normal
Metallic element quality (unit is ppm) needed for rule presoma prepares shell when being 1g, ρ is metallic element needed for preparing shell
Concentration (unit is g/mL) in the solution, saturated concentration of the 0 < ρ≤metallic element in metal salt solution.
Further, metallic element contained by shell be Na, Mg, Ca, Al, Ga, V, Cr, Fe, Ni, Co, Mn, Ti, Zr,
The one or more of Si, Ge.
Further, m (Na)≤6.0wt.%, m (Mg)≤1.0wt.%, m (Al)≤1.0wt.%, m (Ti)≤
1.0wt.%, m (Zr)≤1.0wt.%, m (Ni)≤3.0wt.%, m (Mn)≤3.0wt.%.
Further, ρ≤0.10g/mL.
Further, metal salt is weighed according to the concentration of the metal salt solution, be put into volumetric flask, it is fixed to add solvent
Hold.
Further, the metal salt solution is measured with graduated cylinder, and pours into beaker and adds together with the conventional presoma
Thermal agitation.
Further, the temperature of the baking oven is 100 DEG C.
Further, the solvent is one of deionized water, purity 95vol.% industrial alcohol, dehydrated alcohol.
Further, can decompose under the metal salt high temperature, be acetate, nitrate, meta-aluminate, in organic metal salt
One or more, metallic element needed for the shell contained be Na, Mg, Ca, Al, Ga, V, Cr, Fe, Ni, Co, Mn, Ti, Zr,
The one or more of Si, Ge.
Further, the organic metal salt includes butyl titanate, aluminium isopropoxide.
Further, the temperature when heating stirring is 50~100 DEG C.
The supersaturated solution deposition method that the present invention uses can make the metal salt in solution in a longer heating stirring
In the process, it is gradually precipitated and is coated on conventional presoma surface, forms uniform shell.The presoma of anode material of lithium battery
Usually can all there be hole on surface, and metal salt solution sufficiently infiltrates presoma, other than it can be coated, can also immerse forerunner
Internal portion certain depth.The present invention prepares nucleocapsid using supersaturated solution deposition method using the shape characteristic of conventional presoma
Structured forerunner.Metallic element contained by the shell that this method is prepared not only is distributed across conventional presoma surface, also
A part enters in the hole of conventional presoma, forms gradient distribution.Using this preparation method, the thickness of shell is main
It is determined by the concentration and volume of metal salt solution, gradient distribution is mainly by the infiltration of the pattern and metal salt solution of conventional presoma
Property determine, the ingredient of shell determines by the ingredient of metal salt solution, concentration and volume.By selecting conventional presoma and metal salt
The thickness and ingredient of the adjustable shell of solution.
The presoma of the available core-shell structure of supersaturated solution deposition method provided by the invention, technological operation is simple, right
The requirement of production equipment is low, and the cycle performance and security performance of the anode material of lithium battery of this core-shell structure precursor preparation are bright
The aobvious anode material of lithium battery better than conventional precursor preparation.
Detailed description of the invention
Figure 1A -1B is the pattern SEM figure of the conventional nickel cobalt manganese hydroxide in comparative example 1 and embodiment 1-3, wherein Figure 1A
Amplification factor is 1K, and Figure 1B amplification factor is 10K.
Fig. 2 is the pattern SEM figure of the core-shell structure nickel cobalt manganese hydroxide in embodiment 3.
Fig. 3 A-3B is the electrical property figure of the positive electrode of the core-shell structure nickel cobalt manganese hydroxide preparation in embodiment 3,
Middle Fig. 3 A is charging and discharging curve figure, and Fig. 3 B is circulation volume conservation rate figure.
Fig. 4 A-4C is the pattern SEM figure of the conventional cobaltosic oxide in comparative example 2 and embodiment 4-9, and wherein Fig. 4 A amplifies
Multiple is 1K, and Fig. 4 B amplification factor is 5K, and Fig. 4 C is section pattern.
Fig. 5 A is the pattern SEM figure of the core-shell structure cobaltosic oxide in embodiment 4, and Fig. 5 B is its Al distribution diagram of element.
Fig. 6 A is the pattern SEM figure of the core-shell structure cobaltosic oxide in embodiment 5, and Fig. 6 B is its Al distribution diagram of element.
Fig. 7 A is the pattern SEM figure of the core-shell structure cobaltosic oxide in embodiment 6, and Fig. 7 B is its Al distribution diagram of element.
Fig. 8 A-8B is the electrical property figure of the positive electrode of the core-shell structure cobaltosic oxide preparation in embodiment 6, wherein scheming
8A is charging and discharging curve figure, and Fig. 8 B is circulation volume conservation rate figure.
Fig. 9 A is the pattern SEM figure of the core-shell structure cobaltosic oxide in embodiment 7, and Fig. 9 B is its Ni distribution diagram of element,
Fig. 9 C is its Mn distribution diagram of element.
Figure 10 A is the pattern SEM figure of the core-shell structure cobaltosic oxide in embodiment 8, and Figure 10 B is its Ni Elemental redistribution
Figure, Figure 10 C is its Mn distribution diagram of element.
Figure 11 A is the pattern SEM figure of the core-shell structure cobaltosic oxide in embodiment 9, and Figure 11 B is its Ni Elemental redistribution
Figure, Figure 11 C is its Mn distribution diagram of element.
Figure 12 A-12B is the electrical property figure of the positive electrode of the core-shell structure cobaltosic oxide preparation in embodiment 9, wherein
Figure 12 A is charging and discharging curve figure, and Figure 12 B is circulation volume conservation rate figure.
Figure 13 A-13B is the pattern SEM figure of the conventional cobaltosic oxide in comparative example 3 and embodiment 10, and wherein Figure 13 A is put
Big multiple is 1K, and Figure 13 B amplification factor is 5K.
Figure 14 A-14B is the pattern SEM figure of the conventional nickel cobalt manganese hydroxide in comparative example 3 and embodiment 10, wherein scheming
14A amplification factor is 1K, and Figure 14 B amplification factor is 5K.
Figure 15 is the pattern SEM figure of the mixing presoma in comparative example 3 and embodiment 10, amplification factor 5K.
Figure 16 A is the pattern SEM figure to the core-shell structure mixing presoma in embodiment 10, and Figure 16 B is its Al element point
Butut, Figure 16 C are its Zr distribution diagram of element.
Figure 17 A-17B is the electrical property figure of the positive electrode of the core-shell structure mixing precursor preparation in embodiment 10,
Middle Figure 17 A is charging and discharging curve figure, and Figure 17 B is circulation volume conservation rate figure.
Figure 18 A-18B is the pattern SEM figure of the conventional cobaltosic oxide in comparative example 4 and embodiment 11, and wherein Figure 18 A is put
Big multiple is 1K, and Figure 18 B amplification factor is 5K.
Figure 19 A-19B is the pattern SEM figure of the conventional nickel cobalt manganese hydroxide in comparative example 4 and embodiment 11, wherein scheming
19A amplification factor is 1K, and Figure 19 B amplification factor is 5K.
Figure 20 is the pattern SEM figure of the mixing presoma in comparative example 4 and embodiment 11, amplification factor 1K.
Figure 21 A is the pattern SEM figure to the core-shell structure mixing presoma in embodiment 11, and Figure 21 B is its Al element point
Butut, Figure 21 C are its Zr distribution diagram of element.
Figure 22 A-22B is the electrical property figure of the positive electrode of the core-shell structure mixing precursor preparation in embodiment 11,
Middle Figure 22 A is charging and discharging curve figure, and Figure 22 B is circulation volume conservation rate figure.
Specific embodiment
Illustrate the present invention by way of examples below, but is not construed as limiting the invention.
Comparative example 1
Conventional nickel cobalt manganese hydroxide (Ni:Co:Mn=5:2:3) is mixed with a certain proportion of lithium carbonate, is burnt at 950 DEG C
10h is tied, obtains conventional three-way cellulosic material after broken sieving.The electrical property of this positive electrode is as shown in figs 3 a and 3b.
Embodiment 1
The pattern and distribution of pores situation such as Figure 1A -1B and table 1 of conventional nickel cobalt manganese hydroxide (Ni:Co:Mn=5:2:3)
It is shown, the core-shell structure presoma of Ti=2000ppm is prepared on this basis.Selection butyl titanate does solute, dehydrated alcohol
Solvent is made, the solution 100mL that Ti concentration is 0.01g/mL is made.20g nickel cobalt manganese hydroxide is weighed, is counted according to formula (1)
It calculates shell and needs solution of tetrabutyl titanate 4.0mL.4.0mL solution of tetrabutyl titanate is measured, at room temperature with 400r/min's
Speed stirring, is then poured slowly into nickel cobalt manganese hydroxide, is heated to 50 DEG C, is still stirred with the speed of 400r/min, until
Dehydrated alcohol volatilizees completely.Mixture is put into standing and drying 2h in 100 DEG C of baking ovens, obtains core-shell structure presoma.
The distribution of pores of the conventional nickel cobalt manganese hydroxide of table 1
| Forerunner's body characteristics | BET(m2/g) | Total pore volume (cm3/g) | Average pore size (nm) |
| Conventional nickel cobalt manganese hydroxide | 119.9 | 0.153 | 4.523 |
Embodiment 2
The distribution of pores situation of conventional nickel cobalt manganese hydroxide (Ni:Co:Mn=5:2:3) as shown in Figure 1A -1B and table 1,
The core-shell structure presoma of Ti=2000ppm is prepared on this basis.Selection butyl titanate does solute, and dehydrated alcohol does molten
Agent makes the solution 100mL that Ti concentration is 0.001g/mL.20g nickel cobalt manganese hydroxide is weighed, is calculated according to formula (1)
Shell needs solution of tetrabutyl titanate 40mL.40mL solution of tetrabutyl titanate is measured, is stirred at room temperature with the speed of 200r/min
It mixes, is then poured slowly into nickel cobalt manganese hydroxide, be heated to 100 DEG C, still stirred with the speed of 200r/min, until anhydrous second
Alcohol volatilizees completely.Mixture is put into standing and drying 2h in 100 DEG C of baking ovens, obtains core-shell structure presoma.
Embodiment 3
The distribution of pores situation of conventional nickel cobalt manganese hydroxide (Ni:Co:Mn=5:2:3) as shown in Figure 1A -1B and table 1,
The core-shell structure presoma of Ti=2000ppm is prepared on this basis.Selection butyl titanate does solute, and dehydrated alcohol does molten
Agent makes the solution 100mL that Ti concentration is 0.001g/mL.20g nickel cobalt manganese hydroxide is weighed, is calculated according to formula (1)
Shell needs solution of tetrabutyl titanate 40mL.40mL solution of tetrabutyl titanate is measured, is stirred at room temperature with the speed of 300r/min
It mixes, is then poured slowly into nickel cobalt manganese hydroxide, be heated to 70 DEG C, still stirred with the speed of 300r/min, until anhydrous second
Alcohol volatilizees completely.Mixture is put into standing and drying 2h in 100 DEG C of baking ovens, the pattern of obtained core-shell structure presoma such as Fig. 2
Shown, nickel cobalt manganese hydroxide surfaces are rich in Ti to EDS as the result is shown.By this core-shell structure presoma and a certain proportion of carbonic acid
Lithium mixing obtains three element materials of core-shell structure after 950 DEG C of sintering 10h, broken sieving.The electrical property of this positive electrode
As shown in figs 3 a and 3b.
The Ti content of core-shell structure presoma in embodiment 1,2,3 is as shown in table 2, ICP (inductively coupled plasma spectrum
Generator) the practical Ti content that detects and design Ti content it is close, Ti is almost without loss.
The Ti content of 2 core-shell structure nickel cobalt manganese hydroxide of table
| Ti content | Design value (ppm) | Measured value (ppm) |
| Core-shell structure nickel cobalt manganese hydroxide in embodiment 1 | 2000 | 1967 |
| Core-shell structure nickel cobalt manganese hydroxide in embodiment 2 | 2000 | 1950 |
| Core-shell structure nickel cobalt manganese hydroxide in embodiment 3 | 2000 | 1974 |
Comparative example 2
Conventional cobaltosic oxide is mixed with a certain proportion of lithium carbonate, is obtained after 1000 DEG C of sintering 10h, broken sieving
Conventional cobalt acid lithium material.The electrical property of this positive electrode is as shown in Fig. 8 A-8B, Figure 12 A-12B.
Embodiment 4
The distribution of pores situation of conventional cobaltosic oxide prepares Al=as shown in Fig. 4 A-4C and table 3 on this basis
The core-shell structure presoma of 5000ppm.Selection ANN aluminium nitrate nonahydrate does solute, and deionized water makees solvent, makes Al concentration and is
The solution 100mL of 0.05g/mL.100g cobaltosic oxide is weighed, is calculated according to formula (1) and is prepared shell and need aluminum nitrate molten
Liquid 10mL.10mL aluminum nitrate solution is measured, is stirred at room temperature with the speed of 400r/min, is then poured slowly into four oxidations three
Cobalt is heated to 70 DEG C, is still stirred with the speed of 400r/min, until deionized water is volatilized completely.Mixture is put into 100 DEG C
Standing and drying 4h in baking oven, as indicated by figures 5 a-5b, EDS contains Al small to the pattern of obtained core-shell structure presoma as the result is shown
Grain is evenly distributed on cobaltosic oxide surface.
The distribution of pores of the conventional cobaltosic oxide of table 3
| Forerunner's body characteristics | BET(m2/g) | Total pore volume (cm3/g) | Average pore size (nm) |
| Conventional cobaltosic oxide | 4.191 | 0.021 | 23.753 |
Embodiment 5
The distribution of pores situation of conventional cobaltosic oxide prepares Al=as shown in Fig. 4 A-4C and table 3 on this basis
The core-shell structure presoma of 5000ppm.Selection aluminium isopropoxide does solute, and dehydrated alcohol makees solvent, makes Al concentration and is
The solution 100mL of 0.05g/mL.100g cobaltosic oxide is weighed, is calculated according to formula (1) and is prepared shell and need aluminium isopropoxide
Solution 10mL.10mL aluminium isopropoxide solution is measured, is stirred at room temperature with the speed of 400r/min, is then poured slowly into four oxidations
Three cobalts are heated to 70 DEG C, are still stirred with the speed of 400r/min, until dehydrated alcohol volatilizees completely.Mixture is put into 100
Standing and drying 4h in DEG C baking oven, as shown in figures 6 a-6b, it is small that EDS contains Al to the pattern of obtained core-shell structure presoma as the result is shown
Particle is mainly distributed on cobaltosic oxide surface, locally there is Al enrichment region.
Embodiment 6
The distribution of pores situation of conventional cobaltosic oxide prepares Al=as shown in Fig. 6 A-6B and table 3 on this basis
The core-shell structure presoma of 5000ppm.Selection sodium metaaluminate does solute, and deionized water makees solvent, makes Al concentration and is
The solution 100mL of 0.05g/mL.100g cobaltosic oxide is weighed, is calculated according to formula (1) and is prepared shell and need sodium metaaluminate
Solution 10mL.10mL sodium aluminate solution is measured, is stirred at room temperature with the speed of 400r/min, is then poured slowly into four oxidations
Three cobalts are heated to 70 DEG C, are still stirred with the speed of 400r/min, until deionized water is volatilized completely.Mixture is put into 100
Standing and drying 4h in DEG C baking oven, as illustrated in figures 7 a-b, it is small that EDS contains Al to the pattern of obtained core-shell structure presoma as the result is shown
Particle is evenly distributed on cobaltosic oxide surface.The cobaltosic oxide of this core-shell structure and a certain proportion of lithium carbonate are mixed
It closes, obtains the cobalt acid lithium material of core-shell structure after 1000 DEG C of sintering 10h, broken sieving.The electrical property of this positive electrode is such as
Shown in Fig. 8 A-8B.
The Al content of core-shell structure presoma is as shown in table 4, and the practical Al content that ICP is detected connects with design Al content
Closely, Al is almost without loss.
The Al content of 4 core-shell structure cobaltosic oxide of table
| Al content | Design value (ppm) | Measured value (ppm) |
| Core-shell structure cobaltosic oxide in embodiment 4 | 5000 | 4793 |
| Core-shell structure cobaltosic oxide in embodiment 5 | 5000 | 4832 |
| Core-shell structure cobaltosic oxide in embodiment 6 | 5000 | 4811 |
Embodiment 7
The distribution of pores situation of conventional cobaltosic oxide prepares Ni=as shown in Fig. 6 A-6B and table 3 on this basis
The core-shell structure presoma of 4000ppm, Mn=4000ppm.Selection nickel acetate tetrahydrate and four acetate hydrate manganese do solute, purity
95vol.% industrial alcohol makees solvent, makes the solution 100mL that Ni/Mn total concentration is 0.01g/mL.Weigh the oxidation of 50g tetra- three
Cobalt calculates according to formula (1) and prepares shell and need nickel/manganese solution 40mL.Measure 40mL nickel/manganese solution, at room temperature with
The speed of 300r/min stirs, and is then poured slowly into cobaltosic oxide, is heated to 80 DEG C, is still stirred with the speed of 300r/min
It mixes, until deionized water is volatilized completely.Mixture is put into standing and drying 8h in 100 DEG C of baking ovens, obtained core-shell structure forerunner
The pattern of body is as shown in Figure 9A-9C, and Ni, Mn are evenly distributed on cobaltosic oxide surface to EDS as the result is shown.
Embodiment 8
The distribution of pores situation of conventional cobaltosic oxide prepares Ni=as shown in Fig. 6 A-6B and table 3 on this basis
The core-shell structure presoma of 4000ppm, Mn=4000ppm.Selection nickel acetate tetrahydrate and four acetate hydrate manganese do solute, go from
Sub- water makees solvent, makes the solution 100mL that Ni/Mn total concentration is 0.01g/mL.50g cobaltosic oxide is weighed, according to formula
(1) it calculates and prepares shell and need nickel/manganese solution 40mL.40mL nickel/manganese solution is measured, at room temperature with the speed of 300r/min
Stirring, is then poured slowly into cobaltosic oxide, is heated to 80 DEG C, is still stirred with the speed of 300r/min, until dehydrated alcohol
Volatilization completely.Mixture is put into standing and drying 8h in 100 DEG C of baking ovens, the pattern of obtained core-shell structure presoma such as Figure 10 A-
Shown in 10C, Ni, Mn are evenly distributed on cobaltosic oxide surface to EDS as the result is shown.
Embodiment 9
The distribution of pores situation of conventional cobaltosic oxide prepares Ni=as shown in Fig. 6 A-6B and table 3 on this basis
The core-shell structure presoma of 4000ppm, Mn=4000ppm.Selection Nickelous nitrate hexahydrate and four nitric hydrate manganese do solute, purity
95vol.% industrial alcohol makees solvent, makes the solution 100mL that Ni/Mn total concentration is 0.01g/mL.Weigh the oxidation of 50g tetra- three
Cobalt calculates according to formula (1) and prepares shell and need nickel/manganese solution 40mL.Measure 40mL nickel/manganese solution, at room temperature with
The speed of 300r/min stirs, and is then poured slowly into cobaltosic oxide, is heated to 80 DEG C, is still stirred with the speed of 300r/min
It mixes, until deionized water is volatilized completely.Mixture is put into standing and drying 8h in 100 DEG C of baking ovens, obtained core-shell structure forerunner
The pattern of body is as shown in Figure 11 A-11C, and Ni, Mn are evenly distributed on cobaltosic oxide surface to EDS as the result is shown.By this nucleocapsid knot
The cobaltosic oxide of structure is mixed with a certain proportion of lithium carbonate, obtains core-shell structure after 1000 DEG C of sintering 10h, broken sieving
Cobalt acid lithium material.The electrical property of this positive electrode is as shown in Figure 12 A-12B.
Ni, Mn content of core-shell structure presoma are as shown in table 5, practical Ni, Mn content that ICP is detected and design Ni,
Mn content is close, and Ni, Mn are almost without loss.
Ni, Mn content of 5 core-shell structure cobaltosic oxide of table
Comparative example 3
The distribution of pores situation of regular oxidation cobalt as shown in Figure 13 A-13B and table 6, conventional nickel cobalt manganese hydroxide (Ni:
Co:Mn=8:1:1 distribution of pores) is as shown in Figure 14 A-14B and table 6.By conventional cobaltosic oxide and conventional nickel cobalt manganese hydrogen-oxygen
Compound is mixed according to the ratio of mass ratio 1:1, prepares uniform mixing presoma, and pattern is as shown in figure 15.By four oxidations
The mixture of three cobalts and nickel cobalt manganese hydroxide is mixed with a certain proportion of lithium carbonate, in 850 DEG C of sintering 10h, after being crushed sieving
Obtain cobalt acid lithium and three element mixing materials.The electrical property of this positive electrode is as shown in Figure 17 A-17B.
The distribution of pores of the conventional presoma of table 6
| Forerunner's body characteristics | BET(m2/g) | Total pore volume (cm3/g) | Average pore size (nm) |
| Conventional cobaltosic oxide | 2.35 | 0.0033 | 18.314 |
| Conventional nickel cobalt manganese hydroxide | 83.4 | 0.109 | 4.632 |
Embodiment 10
The distribution of pores situation of regular oxidation cobalt as shown in Figure 13 A-13B and table 6, conventional nickel cobalt manganese hydroxide (Ni:
Co:Mn=8:1:1 distribution of pores) is as shown in Figure 14 A-14B and table 6.By conventional cobaltosic oxide and conventional nickel cobalt manganese hydrogen-oxygen
Compound is mixed according to the ratio of mass ratio 1:1, prepares uniform mixing presoma, and pattern is as shown in figure 15.It is basic herein
The upper core-shell structure mixing presoma for preparing Al=2000ppm/Zr=1000ppm.Selection aluminium isopropoxide, tetrabutyl zirconate do molten
Matter, dehydrated alcohol make solvent, and making Al concentration is the solution 100mL that 0.010g/mL, Zr concentration are 0.005g/mL.It weighs
100g mixing presoma calculates shell according to formula (1) and needs Al/Zr solution 20.0mL.20.0mLAl/Zr solution is measured,
It is stirred at room temperature with the speed of 300r/min, is then poured slowly into the mixture of cobaltosic oxide and nickel cobalt manganese hydroxide,
60 DEG C are heated to, is then stirred with the speed of 400r/min, until dehydrated alcohol volatilizees completely.Mixture is put into 100 DEG C of bakings
Standing and drying 2h in case obtains the pattern of core-shell structure presoma as shown in Figure 16 A-16C, and Al, Zr uniformly divide EDS as the result is shown
Cloth drives body surface face before mixing.
Al, Zr content of core-shell structure mixing presoma are as shown in table 7, practical Al, Zr content that ICP is detected and design
Al, Zr content are close, and Al, Zr are almost without loss.
Al, Zr content of 7 core-shell structure mixing presoma of table
The mixing presoma of this core-shell structure is mixed with a certain proportion of lithium carbonate, in 850 DEG C of sintering 10h, is crushed
The cobalt acid lithium and three element mixing materials of core-shell structure are obtained after sieving.The electrical property of this positive electrode such as Figure 17 A-17B institute
Show.
Comparative example 4
The distribution of pores situation of regular oxidation cobalt as shown in Figure 18 A-18B and table 8, conventional nickel cobalt manganese hydroxide (Ni:
Co:Mn=8:1:1 distribution of pores) is as shown in Figure 19 A-19B and table 8.By conventional cobaltosic oxide and conventional nickel cobalt manganese hydrogen-oxygen
Compound is mixed according to the ratio of mass ratio 1:1, prepares uniform mixing presoma, and pattern is as shown in figure 20.By four oxidations
The mixture of three cobalts and nickel cobalt manganese hydroxide is mixed with a certain proportion of lithium carbonate, in 850 DEG C of sintering 10h, after being crushed sieving
Obtain cobalt acid lithium and three element mixing materials.The electrical property of this positive electrode is as shown in Figure 22 A-22B.
The distribution of pores of the conventional presoma of table 8
| Forerunner's body characteristics | BET(m2/g) | Total pore volume (cm3/g) | Average pore size (nm) |
| Conventional cobaltosic oxide | 4.128 | 0.0032 | 17.164 |
| Conventional nickel cobalt manganese hydroxide | 10.675 | 0.0961 | 5.724 |
Embodiment 11
The distribution of pores situation of regular oxidation cobalt as shown in Figure 18 A-18B and table 8, conventional nickel cobalt manganese hydroxide (Ni:
Co:Mn=8:1:1 distribution of pores) is as shown in Figure 19 A-19B and table 8.By conventional cobaltosic oxide and conventional nickel cobalt manganese hydrogen-oxygen
Compound is mixed according to the ratio of mass ratio 1:1, prepares uniform mixing presoma, and pattern is as shown in figure 20.It is basic herein
The upper core-shell structure mixing presoma for preparing Al=1000ppm/Zr=2000ppm.Selection aluminium isopropoxide, tetrabutyl zirconate do molten
Matter, dehydrated alcohol make solvent, and making Al concentration is the solution 100mL that 0.005g/mL, Zr concentration are 0.010g/mL.It weighs
100g mixing presoma calculates shell according to formula (1) and needs Al/Zr solution 20.0mL.20.0mLAl/Zr solution is measured,
It is stirred at room temperature with the speed of 300r/min, is then poured slowly into the mixture of cobaltosic oxide and nickel cobalt manganese hydroxide,
60 DEG C are heated to, is then stirred with the speed of 400r/min, until dehydrated alcohol volatilizees completely.Mixture is put into 100 DEG C of bakings
Standing and drying 2h in case obtains the pattern of core-shell structure presoma as shown in Figure 21 A-21C, and Al, Zr uniformly divide EDS as the result is shown
Cloth drives body surface face before mixing.
Al, Zr content of core-shell structure mixing presoma are as shown in table 9, practical Al, Zr content that ICP is detected and design
Al, Zr content are close, and Al, Zr are almost without loss.
Al, Zr content of 9 core-shell structure mixing presoma of table
The mixing presoma of this core-shell structure is mixed with a certain proportion of lithium carbonate, in 850 DEG C of sintering 10h, is crushed
The cobalt acid lithium and three element mixing materials of core-shell structure are obtained after sieving.The electrical property of this positive electrode such as Figure 22 A-22B institute
Show.
It is of the invention used for core-shell structure presoma evaluation method is as follows:
With the surface topography of scanning electron microscope (JEOL, JSM-7500F) observation core-shell structure presoma.
By the core-shell structure presoma and conductive carbon material and binder Vingon according to mass ratio 90:5:5's
Ratio is mixed, and N-Methyl pyrrolidone is added dropwise and is ground to paste and is coated in copper foil surface, test is made after 120 DEG C of drying
Pole piece.The section that pole piece is polished with cross section polishing machine (JEOL, IB-19510CP), then uses scanning electron microscope
The section pattern of (JEOL, JSM-7500F) observation core-shell structure presoma.
With Inductively coupled plasma optical emission spectrometer (the silent winged generation that science and technology of match, ICAP6300) detection core-shell structure presoma
In shell element content.
Core-shell structure presoma and lithium carbonate are mixed, nucleocapsid is prepared in the then sintering in section's crystalline substance furnace (KSL-1200X)
The positive electrode of structure.
By the positive electrode and conductive carbon material and binder Vingon according to mass ratio 90:5:5 ratio into
Row mixing is added dropwise N-Methyl pyrrolidone and is ground to paste and is coated in aluminium foil surface, it is electric that anode test is made after 120 DEG C of drying
Pole.Experimental cell selects metal lithium sheet to electrode (reference electrode), and experimental cell selects CR2032 type battery component to carry out group
Dress, experimental cell, which is placed in insulating box and connects charge-discharge test instrument, carries out charge-discharge test.
Three element materials of the core-shell structure precursor preparation in embodiment 3,3.0~4.25V passes through in half-cell
Resulting specific capacity-the voltage curve of 0.1C/0.1C charge-discharge test and in 4.25V with the resulting appearance of the charge-discharge magnification of 1C/1C
Conservation rate-cycle-index curve is measured, as shown in figs. 4 a-4 c, the specific discharge capacity of this material reaches 163mAh/g, with comparative example
1 quite, and capacity retention ratio of the circulation after 100 weeks reaches 88.5%, is higher than comparative example 1.
The cobalt acid lithium material of core-shell structure precursor preparation of the shell rich in Al in embodiment 6,3.0 in half-cell~
4.5V is by the resulting specific capacity-voltage curve of 0.2C/0.2C charge-discharge test and in 4.6V with the charge and discharge of 0.7C/0.7C times
The resulting capacity retention ratio of rate-cycle-index curve, as shown in figures 8 a-8b, the specific discharge capacity of this material reaches 186mAh/
G, than the low 4mAh/g of comparative example 2, but the capacity retention ratio after 4.6V is recycled 50 weeks reaches 92%, is higher than comparative example 2.
The cobalt acid lithium material of core-shell structure precursor preparation of the shell rich in Ni/Mn in embodiment 9, in half-cell
3.0~4.5V passes through the resulting specific capacity-voltage curve of 0.2C/0.2C charge-discharge test and the filling with 0.7C/0.7C in 4.6V
The resulting capacity retention ratio of discharge-rate-cycle-index curve, as shown in Figure 12 A-12B, the specific discharge capacity of this material with
Comparative example 2 is suitable, but the capacity retention ratio after 4.6V is recycled 50 weeks reaches 90%, is higher than comparative example 2.
The cobalt acid lithium material of core-shell structure precursor preparation of the shell rich in Al/Zr in embodiment 10, in half-cell
3.0~4.25V is by the resulting specific capacity-voltage curve of 0.1C/0.1C charge-discharge test and in 4.25V with 0.5C/0.5C's
The resulting capacity retention ratio of charge-discharge magnification-cycle-index curve, as shown in Figure 17 A-17B, the specific discharge capacity of this material
Quite with comparative example 3, but the capacity retention ratio after 4.25V is recycled 100 weeks reaches 90%, is higher than comparative example 3.
The cobalt acid lithium material of core-shell structure precursor preparation of the shell rich in Al/Zr in embodiment 11, in half-cell
3.0~4.25V is by the resulting specific capacity-voltage curve of 0.1C/0.1C charge-discharge test and in 4.25V with 0.5C/0.5C's
The resulting capacity retention ratio of charge-discharge magnification-cycle-index curve, as shown in Figure 22 A-22B, the specific discharge capacity of this material
About 2mAh/g lower than comparative example 4, but the capacity retention ratio after 4.25V is recycled 100 weeks reaches 93%, is higher than comparative example 4.
The above embodiments are merely illustrative of the technical solutions of the present invention rather than is limited, the ordinary skill of this field
Personnel can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the spirit and scope of the present invention, this
The protection scope of invention should be subject to described in claims.
Claims (10)
1. a kind of preparation method of the core-shell structure presoma of anode material of lithium battery, step include:
Metal salt and solvent are weighed, metallic element needed for which contains shell to be prepared is configured to metal salt solution；
It weighs by least one of cobaltosic oxide, nickel cobalt manganese hydroxide as conventional presoma, is slowly added into above-mentioned
In metal salt solution, heating stirring obtains mixture until solvent volatilizees completely to solution supersaturation；
Said mixture is put into standing and drying in baking oven, after being completely dried, is coated with a shell on conventional presoma surface, i.e.,
Obtain core-shell structure presoma.
2. the method as described in claim 1, which is characterized in that can decompose under the metal salt high temperature, be acetate, nitric acid
One or more of salt, meta-aluminate, organic metal salt, the metallic element be Na, Mg, Ca, Al, Ga, V, Cr, Fe, Ni,
The one or more of Co, Mn, Ti, Zr, Si, Ge.
3. method according to claim 2, which is characterized in that the organic metal salt includes butyl titanate, aluminium isopropoxide.
4. the method as described in claim 1, which is characterized in that the solvent is deionized water, purity 95vol.% industry wine
One of essence, dehydrated alcohol.
5. the method as described in claim 1, which is characterized in that the concentration of metallic element is small greater than 0 in the metal salt solution
In equal to its saturated concentration.
6. the method as described in claim 1, which is characterized in that the volume of the metal salt solution is calculated by the following formula
It arrives:
V=W × m × 10-6/ρ；
Wherein, V is the volume of metal salt solution, and unit is mL；W is the quality of conventional presoma, and unit is g；M is conventional forerunner
Metallic element quality needed for body prepares shell when being 1g, unit is ppm；ρ is metallic element needed for preparing shell in solution
In concentration, unit is g/mL.
7. method as claimed in claim 6, which is characterized in that m (Na)≤6.0wt.%, m (Mg)≤1.0wt.%, m (Al)
≤ 1.0wt.%, m (Ti)≤1.0wt.%, m (Zr)≤1.0wt.%, m (Ni)≤3.0wt.%, m (Mn)≤3.0wt.%.
8. method as claimed in claim 6, which is characterized in that ρ≤0.10g/mL.
9. the method as described in claim 1, which is characterized in that weigh metal salt according to the concentration of the metal salt solution, put
Enter in volumetric flask, adds solvent constant volume；The metal salt solution is measured with graduated cylinder, and is poured into together with the conventional presoma
Heating stirring in beaker.
10. the method as described in claim 1, which is characterized in that the temperature of the baking oven is 100 DEG C, when the heating stirring
Temperature be 50~100 DEG C.
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