CN109962217A - Lithium manganese silicate coated nickel-cobalt-manganese ternary material and preparation method thereof - Google Patents
Lithium manganese silicate coated nickel-cobalt-manganese ternary material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a lithium manganese silicate coated nickel-cobalt-manganese ternary material and a preparation method thereof, wherein the chemical general formula of the material is Li(1+4n)NixCoyMn(1‑x‑y+n)SinO2+4nWherein x is more than or equal to 0.6 and less than or equal to 0.7, y is more than or equal to 0.1 and less than or equal to 0.2, and n is more than or equal to 0 and less than or equal to 0.05; the method prepares a primary sintered product LiNixCoyMn(1‑x‑y)O2And then the primary sintered product LiNixCoyMn(1‑x‑y)O2Adding the lithium manganese silicate into a lithium manganese silicate coating solution, and finally sintering to obtain a lithium manganese silicate coated lithium nickel cobalt manganese oxide ternary material; therefore, the invention utilizes the advantages of high capacity and high safety of the lithium manganese silicate to coat the lithium manganese silicate on the surface of the ternary material, thereby improving the capacity and safety of the material; and by combining the longer cycle life of the ternary material, a more ideal power battery anode material can be obtained.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding
And preparation method thereof.
Background technique
Lithium ion battery is widely answered with its high operating voltage, low self discharge effect and good cycle performance
With communication, portable computer and electronic energy storage devices；Currently, pure power vehicle, compared with fuel vehicle, course continuation mileage is still pure
One of short slab of electric vehicle, thus raising positive electrode capacity is extremely urgent, especially to anode material for lithium-ion batteries
More stringent requirements are proposed for energy density, therefore, it is necessary to develop new anode material for lithium-ion batteries.
It in recent years, is that current application is the widest by positive electrode prepared by raw material of the oxide of the oxide of cobalt and nickel
It is general, but the material as prepared by cobalt and nickel safety, material source, in terms of all asked there are to be solved
Topic；And for other positive electrodes, also have and respectively needs improved aspect, such as: LiMn2O4It is cheap, security performance
It is good, but its theoretical capacity is not high, and cycle performance and thermal stability are poor；LiFePO4Though there is good thermal stability and follow
Ring performance and higher specific energy and safety, but lower electronic conductivity and lithium ion diffusion rate are as its continuation
Study a big obstacle of application；For this purpose, Nyt é n etc. has been put forward for the first time polyanionic silicate anodal material, and wherein silicic acid
Manganese lithium (Li2MnSiO4) is with the height ratio capacity of its 333mAh/g, it is considered to be optimal anode material for lithium-ion batteries.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is intended to provide a kind of nickel cobalt manganese three of manganese silicate of lithium cladding
First material and preparation method thereof.
The embodiment of the present invention provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding, chemical general formula Li(1+4n)
NixCoyMn(1-x-y+n)SinO2+4n, wherein 0.6≤x≤0.7,0.1≤y≤0.2,0≤n≤0.05.
The preparation side of the nickel-cobalt-manganese ternary material for the manganese silicate of lithium cladding that the present invention also provides a kind of as described in above scheme
Method, method are implemented by following steps:
Step 1, by NixCoyMn(1-x-y)(OH)2Ternary precursor and lithium source according to lithium source mole with
NixCoyMn(1-x-y)(OH)2The ratio between the sum of mole of nickel cobalt manganese is 1.00≤Li:(Ni+Co+Mn in ternary precursor)≤
1.10 uniformly mixing, are then sintered under oxygen atmosphere, finally pulverize and sieve, obtain once sintered product LiNixCoyMn(1-x-y)
O2；
Step 2, lithium salts is dissolved in enough water, is once stirred, obtained the first solution, then add to first solution
Entering Li:Si:Mn molar ratio in silica and manganese salt to solution is 4:1:1, carries out secondary agitation and stands, obtains manganese silicate of lithium
Cladding solution；
Step 3, by the once sintered product LiNixCoyMn(1-x-y)O2It is added in manganese silicate of lithium cladding solution, obtains the
Second solution is sintered by two solution, obtains the cobalt nickel lithium manganate ternary material of manganese silicate of lithium cladding.
In above scheme, lithium source described in the step 1 is at least one of lithium carbonate, lithium hydroxide or lithium oxalate.
In above scheme, sintering temperature is 700~900 DEG C in the step 1, and sintering time is 10~20h.
In above scheme, the addition rate of silica described in the step 2 and manganese salt be per hour 0.1~
1.0mol/L。
In above scheme, silica described in the step 2 is nanometer grade powder, the granularity of the SiO 2 powder
Range is 50~300nm, and the manganese salt is nano-scale particle, and the particle size range of the manganese salt particle is 50~1000nm.
In above scheme, lithium salts described in the step 2 is lithium hydroxide or lithium oxalate, and the manganese salt is manganese carbonate, grass
One of sour manganese or manganese oxide.
In above scheme, the time once stirred of the step 2 is 1~2h, the stirring temperature of the secondary agitation
Degree is 50~150 DEG C.
In above scheme, the solid-liquid mass ratio of the second solution described in the step 3 is 3:1~1:5.
In above scheme, sintering temperature is 500~800 DEG C in the step 3, and sintering time is 5~10h.
Compared with prior art, the invention proposes a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding and its preparation sides
Method, chemical general formula Li(1+4n)NixCoyMn(1-x-y+n)SinO2+4n, wherein 0.6≤x≤0.7,0.1≤y≤0.2,0≤n≤
0.05；This method is by preparing once sintered product LiNixCoyMn(1-x-y)O2, then by the once sintered product
LiNixCoyMn(1-x-y)O2It is added in manganese silicate of lithium cladding solution, finally sintering obtains the nickle cobalt lithium manganate of manganese silicate of lithium cladding
Ternary material；In this way, the present invention utilizes the advantages of high capacity and high security of manganese silicate of lithium, coated and ternary material table
Capacity, the safety of material can be improved in face；And pass through the longer cycle life for combining ternary material itself to have, energy
Enough obtain ideal power battery anode material.
Detailed description of the invention
Fig. 1 is a kind of nickel-cobalt-manganese ternary material and preparation method thereof for manganese silicate of lithium cladding that the embodiment of the present invention 1 provides
Flash-over characteristic comparison diagram.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments and attached drawing, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The embodiment of the present invention provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding, chemical general formula Li(1+4n)
NixCoyMn(1-x-y+n)SinO2+4n, wherein 0.6≤x≤0.7,0.1≤y≤0.2,0≤n≤0.05.
The embodiment of the present invention also provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding as described in above scheme
Preparation method, method are implemented by following steps:
Step 1, by NixCoyMn(1-x-y)(OH)2Ternary precursor is uniformly mixed with lithium source, then under oxygen atmosphere
It is sintered 10~20h at 700~900 DEG C, finally pulverizes and sieves, obtains once sintered product LiNixCoyMn(1-x-y)O2；
Wherein, the mole and Ni of lithium sourcexCoyMn(1-x-y)(OH)2In ternary precursor the sum of mole of nickel cobalt manganese it
Than for 1.00≤Li:(Ni+Co+Mn)≤1.10；
Wherein, the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate；
Step 2, lithium salts is dissolved in enough water, carries out 1~2h of primary stirring, the first solution is obtained, then with per hour 0.1
It is 4:1 that Li:Si:Mn molar ratio in silica and manganese salt to solution, which is added, to first solution in the rate of~1.0mol/L:
1, secondary agitation is carried out at 50~150 DEG C and is stood, and manganese silicate of lithium cladding solution is obtained；
Wherein, silica described in the step 2 is nanometer grade powder, and the particle size range of the SiO 2 powder is
50~300nm, the manganese salt are nano-scale particle, and the particle size range of the manganese salt particle is 50~1000nm；
Wherein, lithium salts described in the step 2 be lithium hydroxide or lithium oxalate, the manganese salt be manganese carbonate, manganese oxalate or
One of manganese oxide；
Step 3, by the once sintered product LiNixCoyMn(1-x-y)O2Manganese silicate of lithium cladding solution after being added to dilution
It is interior, the second solution is obtained, the solid-liquid mass ratio of the second solution of control is 3:1~1:5, and then stirring is evaporated, finally, after being evaporated
Second solution be put into sintering furnace, at 500~800 DEG C, be sintered 5~10h, obtain manganese silicate of lithium cladding nickel cobalt manganese
Sour lithium ternary material.
The invention proposes a kind of nickel-cobalt-manganese ternary materials and preparation method thereof of manganese silicate of lithium cladding, and chemical general formula is
Li(1+4n)NixCoyMn(1-x-y+n)SinO2+4n, wherein 0.6≤x≤0.7,0.1≤y≤0.2,0≤n≤0.05；This method passes through
Prepare once sintered product LiNixCoyMn(1-x-y)O2, then by the once sintered product LiNixCoyMn(1-x-y)O2It is added to silicic acid
In manganese lithium cladding solution, finally sintering obtains the cobalt nickel lithium manganate ternary material of manganese silicate of lithium cladding；In this way, the present invention utilizes silicon
The advantages of high capacity and high security of sour manganese lithium, coated with ternary material surface, capacity, the safety of material can be improved
Property；And by the longer cycle life for combining ternary material itself to have, ideal power battery can obtained just
Pole material.
The present invention can make covering be evenly affixed to material surface by the way of wet process cladding, and cladding thickness is uniform；
Sintering temperature is chosen for 500~800 DEG C, and lithium salts, manganese salt, silicon dioxde reaction can be made to generate manganese silicate of lithium, and be coated on nickel
The surface of cobalt manganic acid lithium ternary material；The theoretical specific capacity of covering material manganous silicate itself can reach 330330mAh/g simultaneously,
Higher than common ternary material~270mAh/g specific capacity, also, Si-O key thermal stability with higher at present, Ke Yiti
The security performance of high material；In addition, Mn element itself is cheap, environmental-friendly in manganese silicate of lithium material.
Embodiment 1
The embodiment of the present invention provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding, and chemical general formula is
Li1.04Ni0.6Co0.2Mn0.21Si0.01O2.04。
The embodiment of the present invention also provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding as described in above scheme
Preparation method, method are implemented by following steps:
Step 1, by Ni0.6Co0.2Mn0.2(OH)2Ternary precursor is uniformly mixed with lithium source, then under oxygen atmosphere
It is sintered 15h at 800 DEG C, finally pulverizes and sieves, obtains once sintered product LiNi0.6Co0.2Mn0.2O2；
Wherein, the mole and Ni of lithium sourcexCoyMn(1-x-y)(OH)2In ternary precursor the sum of mole of nickel cobalt manganese it
Than for 1.00≤Li:(Ni+Co+Mn)≤1.10；
Wherein, the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate；
Step 2, lithium salts is dissolved in enough water, carries out 1~2h of primary stirring, the first solution is obtained, then with per hour
It is 4:1:1 that Li:Si:Mn molar ratio in silica and manganese salt to solution, which is added, to first solution in the rate of 0.1mol/L,
Secondary agitation is carried out at 100 DEG C and is stood, and manganese silicate of lithium cladding solution is obtained；
Wherein, silica described in the step 2 is nanometer grade powder, and the manganese salt is nano-scale particle；
Wherein, lithium salts described in the step 2 be lithium hydroxide or lithium oxalate, the manganese salt be manganese carbonate, manganese oxalate or
One of manganese oxide；
Step 3, by the once sintered product LiNi0.6Co0.2Mn0.2O2Manganese silicate of lithium cladding solution after being added to dilution
It is interior, the second solution is obtained, the solid-liquid mass ratio of the second solution of control is 3:1~1:5, and then stirring is evaporated, finally, after being evaporated
Second solution be put into sintering furnace, at 650 DEG C, be sintered 5h, obtain manganese silicate of lithium cladding nickle cobalt lithium manganate ternary
Material.
It is discharged using the 622 nickel-cobalt-manganese ternary material of cladded type and traditional 622 nickel-cobalt-manganese ternary materials of above-mentioned acquisition
Performance comparison, flash-over characteristic comparison diagram, as shown in Figure 1, as seen from the figure, curve 1 is 622 nickel of cladded type that the present invention obtains
Cobalt-manganese ternary material, at 2.75-4.3V and normal temperature condition, when 1C charging 2C discharges, specific discharge capacity reaches 170mAh/g, and
Curve 2 is traditional 622 nickel-cobalt-manganese ternary materials, and at 2.75-4.3V and normal temperature condition, when 1C charging 2C discharges, discharge specific volume
Amount only reaches 159mAh/g, it is seen then that the cladding of manganese silicate of lithium significantly improves the theoretical specific capacity of material
Embodiment 2
The embodiment of the present invention provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding, and chemical general formula is
Li1.08Ni0.6Co0.2Mn0.22Si0.02O2.08。
The embodiment of the present invention also provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding as described in above scheme
Preparation method, method are implemented by following steps:
Step 1, by Ni0.6Co0.2Mn0.2(OH)2Ternary precursor is uniformly mixed with lithium source, then under oxygen atmosphere
It is sintered 15h at 800 DEG C, finally pulverizes and sieves, obtains once sintered product LiNi0.6Co0.2Mn0.2O2；
Wherein, the mole and Ni of lithium source0.6Co0.2Mn0.2(OH)2In ternary precursor the sum of mole of nickel cobalt manganese it
Than for 1.00≤Li:(Ni+Co+Mn)≤1.10；
Wherein, the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate；
Step 2, lithium salts is dissolved in enough water, carries out 1~2h of primary stirring, the first solution is obtained, then with per hour
It is 4:1:1 that Li:Si:Mn molar ratio in silica and manganese salt to solution, which is added, to first solution in the rate of 0.5mol/L,
Secondary agitation is carried out at 100 DEG C and is stood, and manganese silicate of lithium cladding solution is obtained；
Wherein, silica described in the step 2 is nanometer grade powder, and the manganese salt is nano-scale particle；
Wherein, lithium salts described in the step 2 be lithium hydroxide or lithium oxalate, the manganese salt be manganese carbonate, manganese oxalate or
One of manganese oxide；
Step 3, by the once sintered product LiNi0.6Co0.2Mn0.2O2Manganese silicate of lithium cladding solution after being added to dilution
It is interior, the second solution is obtained, the solid-liquid mass ratio of the second solution of control is 3:1~1:5, and then stirring is evaporated, finally, after being evaporated
Second solution be put into sintering furnace, at 650 DEG C, be sintered 5h, obtain manganese silicate of lithium cladding nickle cobalt lithium manganate ternary
Material.
It is discharged using the 622 nickel-cobalt-manganese ternary material of cladded type and traditional 622 nickel-cobalt-manganese ternary materials of above-mentioned acquisition
Performance comparison, flash-over characteristic comparison diagram is similar to Example 1, the 622 nickel-cobalt-manganese ternary material of cladded type that the present invention obtains,
Under 2.75-4.3V and normal temperature condition, 1C charge 2C electric discharge when, specific discharge capacity reaches 172mAh/g, and traditional 622 nickel cobalt manganeses three
First material, at 2.75-4.3V and normal temperature condition, when 1C charging 2C discharges, specific discharge capacity only reaches 159mAh/g, it is seen then that
The cladding of manganese silicate of lithium significantly improves the theoretical specific capacity of material.
Embodiment 3
The embodiment of the present invention provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding, and chemical general formula is
Li1.12Ni0.6Co0.2Mn0.23Si0.03O2.12。
The embodiment of the present invention also provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding as described in above scheme
Preparation method, method are implemented by following steps:
Step 1, by Ni0.6Co0.2Mn0.2(OH)2Ternary precursor is uniformly mixed with lithium source, then under oxygen atmosphere
It is sintered 15h at 800 DEG C, finally pulverizes and sieves, obtains once sintered product LiNi0.6Co0.2Mn0.2O2；
Wherein, the mole and Ni of lithium source0.6Co0.2Mn0.2(OH)2In ternary precursor the sum of mole of nickel cobalt manganese it
Than for 1.00≤Li:(Ni+Co+Mn)≤1.10；
Wherein, the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate；
Step 2, lithium salts is dissolved in enough water, carries out 1~2h of primary stirring, the first solution is obtained, then with per hour
It is 4:1:1 that Li:Si:Mn molar ratio in silica and manganese salt to solution, which is added, to first solution in the rate of 1.0mol/L,
Secondary agitation is carried out at 100 DEG C and is stood, and manganese silicate of lithium cladding solution is obtained；
Wherein, silica described in the step 2 is nanometer grade powder, and the manganese salt is nano-scale particle；
Wherein, lithium salts described in the step 2 be lithium hydroxide or lithium oxalate, the manganese salt be manganese carbonate, manganese oxalate or
One of manganese oxide；
Step 3, by the once sintered product LiNi0.6Co0.2Mn0.2O2Manganese silicate of lithium cladding solution after being added to dilution
It is interior, the second solution is obtained, the solid-liquid mass ratio of the second solution of control is 3:1~1:5, and then stirring is evaporated, finally, after being evaporated
Second solution be put into sintering furnace, at 650 DEG C, be sintered 5h, obtain manganese silicate of lithium cladding nickle cobalt lithium manganate ternary
Material.
It is discharged using the 622 nickel-cobalt-manganese ternary material of cladded type and traditional 622 nickel-cobalt-manganese ternary materials of above-mentioned acquisition
Performance comparison, flash-over characteristic comparison diagram is similar to Example 1, the 622 nickel-cobalt-manganese ternary material of cladded type that the present invention obtains,
Under 2.75-4.3V and normal temperature condition, 1C charge 2C electric discharge when, specific discharge capacity reaches 170mAh/g, and traditional 622 nickel cobalt manganeses three
First material, at 2.75-4.3V and normal temperature condition, when 1C charging 2C discharges, specific discharge capacity only reaches 159mAh/g, it is seen then that
The cladding of manganese silicate of lithium significantly improves the theoretical specific capacity of material.
Embodiment 4
The embodiment of the present invention provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding, and chemical general formula is
Li1.16Ni0.6Co0.2Mn0.24Si0.04O2.16。
The embodiment of the present invention also provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding as described in above scheme
Preparation method, method are implemented by following steps:
Step 1, by Ni0.6Co0.2Mn0.2(OH)2Ternary precursor is uniformly mixed with lithium source, then under oxygen atmosphere
It is sintered 20h at 700 DEG C, finally pulverizes and sieves, obtains once sintered product LiNi0.6Co0.2Mn0.2O2；
Wherein, the mole and Ni of lithium source0.6Co0.2Mn0.2(OH)2In ternary precursor the sum of mole of nickel cobalt manganese it
Than for 1.00≤Li:(Ni+Co+Mn)≤1.10；
Wherein, the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate；
Step 2, lithium salts is dissolved in enough water, carries out 1~2h of primary stirring, the first solution is obtained, then with per hour
It is 4:1:1 that Li:Si:Mn molar ratio in silica and manganese salt to solution, which is added, to first solution in the rate of 0.8mol/L,
Secondary agitation is carried out at 100 DEG C and is stood, and manganese silicate of lithium cladding solution is obtained；
Wherein, silica described in the step 2 is nanometer grade powder, and the manganese salt is nano-scale particle；
Wherein, lithium salts described in the step 2 be lithium hydroxide or lithium oxalate, the manganese salt be manganese carbonate, manganese oxalate or
One of manganese oxide；
Step 3, by the once sintered product LiNi0.6Co0.2Mn0.2O2Manganese silicate of lithium cladding solution after being added to dilution
It is interior, the second solution is obtained, the solid-liquid mass ratio of the second solution of control is 3:1~1:5, and then stirring is evaporated, finally, after being evaporated
Second solution be put into sintering furnace, at 650 DEG C, be sintered 8h, obtain manganese silicate of lithium cladding nickle cobalt lithium manganate ternary
Material.
It is discharged using the 622 nickel-cobalt-manganese ternary material of cladded type and traditional 622 nickel-cobalt-manganese ternary materials of above-mentioned acquisition
Performance comparison, flash-over characteristic comparison diagram is similar to Example 1, the 622 nickel-cobalt-manganese ternary material of cladded type that the present invention obtains,
Under 2.75-4.3V and normal temperature condition, 1C charge 2C electric discharge when, specific discharge capacity reaches 175mAh/g, and traditional 622 nickel cobalt manganeses three
First material, at 2.75-4.3V and normal temperature condition, when 1C charging 2C discharges, specific discharge capacity only reaches 159mAh/g, it is seen then that
The cladding of manganese silicate of lithium significantly improves the theoretical specific capacity of material.
Embodiment 5
The embodiment of the present invention provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding, and chemical general formula is
Li1.2Ni0.6Co0.2Mn0.25Si0.05O2.2。
The embodiment of the present invention also provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding as described in above scheme
Preparation method, method are implemented by following steps:
Step 1, by Ni0.6Co0.2Mn0.2(OH)2Ternary precursor is uniformly mixed with lithium source, then under oxygen atmosphere
It is sintered 15h at 800 DEG C, finally pulverizes and sieves, obtains once sintered product LiNixCoyMn(1-x-y)O2；
Wherein, the mole and Ni of lithium source0.6Co0.2Mn0.2(OH)2In ternary precursor the sum of mole of nickel cobalt manganese it
Than for 1.00≤Li:(Ni+Co+Mn)≤1.10；
Wherein, the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate；
Step 2, lithium salts is dissolved in enough water, carries out 1~2h of primary stirring, the first solution is obtained, then with per hour
It is 4:1:1 that Li:Si:Mn molar ratio in silica and manganese salt to solution, which is added, to first solution in the rate of 0.8mol/L,
Secondary agitation is carried out at 100 DEG C and is stood, and manganese silicate of lithium cladding solution is obtained；
Wherein, silica described in the step 2 is nanometer grade powder, and the manganese salt is nano-scale particle；
Wherein, lithium salts described in the step 2 be lithium hydroxide or lithium oxalate, the manganese salt be manganese carbonate, manganese oxalate or
One of manganese oxide；
Step 3, by the once sintered product LiNi0.6Co0.2Mn0.2O2Manganese silicate of lithium cladding solution after being added to dilution
It is interior, the second solution is obtained, the solid-liquid mass ratio of the second solution of control is 3:1~1:5, and then stirring is evaporated, finally, after being evaporated
Second solution be put into sintering furnace, at 650 DEG C, be sintered 8h, obtain manganese silicate of lithium cladding nickle cobalt lithium manganate ternary
Material.
It is discharged using the 622 nickel-cobalt-manganese ternary material of cladded type and traditional 622 nickel-cobalt-manganese ternary materials of above-mentioned acquisition
Performance comparison, flash-over characteristic comparison diagram is similar to Example 1, the 622 nickel-cobalt-manganese ternary material of cladded type that the present invention obtains,
Under 2.75-4.3V and normal temperature condition, 1C charge 2C electric discharge when, specific discharge capacity reaches 173mAh/g, and traditional 622 nickel cobalt manganeses three
First material, at 2.75-4.3V and normal temperature condition, when 1C charging 2C discharges, specific discharge capacity only reaches 159mAh/g, it is seen then that
The cladding of manganese silicate of lithium significantly improves the theoretical specific capacity of material.
Embodiment 6
The embodiment of the present invention provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding, and chemical general formula is
Li1.04Ni0.7Co0.1Mn0.21Si0.01O2.04, wherein 0.6≤x≤0.7,0.1≤y≤0.2,0≤n≤0.05.
The embodiment of the present invention also provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding as described in above scheme
Preparation method, method are implemented by following steps:
Step 1, by Ni0.7Co0.1Mn0.2(OH)2Ternary precursor is uniformly mixed with lithium source, then under oxygen atmosphere
It is sintered 10h at 900 DEG C, finally pulverizes and sieves, obtains once sintered product LiNi0.7Co0.1Mn0.2O2；
Wherein, the mole and Ni of lithium source0.7Co0.1Mn0.2(OH)2In ternary precursor the sum of mole of nickel cobalt manganese it
Than for 1.00≤Li:(Ni+Co+Mn)≤1.10；
Wherein, the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate；
Step 2, lithium salts is dissolved in enough water, carries out 1~2h of primary stirring, the first solution is obtained, then with per hour
It is 4:1:1 that Li:Si:Mn molar ratio in silica and manganese salt to solution, which is added, to first solution in the rate of 0.8mol/L,
Secondary agitation is carried out at 100 DEG C and is stood, and manganese silicate of lithium cladding solution is obtained；
Wherein, silica described in the step 2 is nanometer grade powder, and the manganese salt is nano-scale particle；
Wherein, lithium salts described in the step 2 be lithium hydroxide or lithium oxalate, the manganese salt be manganese carbonate, manganese oxalate or
One of manganese oxide；
Step 3, by the once sintered product LiNi0.7Co0.1Mn0.2O2Manganese silicate of lithium cladding solution after being added to dilution
It is interior, the second solution is obtained, the solid-liquid mass ratio of the second solution of control is 3:1~1:5, and then stirring is evaporated, finally, after being evaporated
Second solution be put into sintering furnace, at 650 DEG C, be sintered 8h, obtain manganese silicate of lithium cladding nickle cobalt lithium manganate ternary
Material.
It is discharged using the 712 nickel-cobalt-manganese ternary material of cladded type and traditional 712 nickel-cobalt-manganese ternary materials of above-mentioned acquisition
Performance comparison, flash-over characteristic comparison diagram is similar to Example 1, the 712 nickel-cobalt-manganese ternary material of cladded type that the present invention obtains,
Under 2.75-4.3V and normal temperature condition, 1C charge 2C electric discharge when, specific discharge capacity reaches 172mAh/g, and traditional 712 nickel cobalt manganeses three
First material, at 2.75-4.3V and normal temperature condition, when 1C charging 2C discharges, specific discharge capacity only reaches 159mAh/g, it is seen then that
The cladding of manganese silicate of lithium significantly improves the theoretical specific capacity of material.
Embodiment 7
The embodiment of the present invention provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding, and chemical general formula is
Li1.08Ni0.7Co0.1Mn0.22Si0.02O2.08。
The embodiment of the present invention also provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding as described in above scheme
Preparation method, method are implemented by following steps:
Step 1, by Ni0.7Co0.1Mn0.2(OH)2Ternary precursor is uniformly mixed with lithium source, then under oxygen atmosphere
It is sintered 16h at 800 DEG C, finally pulverizes and sieves, obtains once sintered product LiNi0.7Co0.1Mn0.2O2；
Wherein, the mole and Ni of lithium source0.7Co0.1Mn0.2(OH)2In ternary precursor the sum of mole of nickel cobalt manganese it
Than for 1.00≤Li:(Ni+Co+Mn)≤1.10；
Wherein, the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate；
Step 2, lithium salts is dissolved in enough water, carries out primary stirring 1h, the first solution is obtained, then with per hour
It is 4:1:1 that Li:Si:Mn molar ratio in silica and manganese salt to solution, which is added, to first solution in the rate of 1.5mol/L,
Secondary agitation is carried out at 50 DEG C and is stood, and manganese silicate of lithium cladding solution is obtained；
Wherein, silica described in the step 2 is nanometer grade powder, and the manganese salt is nano-scale particle；
Wherein, lithium salts described in the step 2 be lithium hydroxide or lithium oxalate, the manganese salt be manganese carbonate, manganese oxalate or
One of manganese oxide；
Step 3, by the once sintered product LiNi0.7Co0.1Mn0.2O2Manganese silicate of lithium cladding solution after being added to dilution
It is interior, the second solution is obtained, the solid-liquid mass ratio of the second solution of control is 3:1~1:5, and then stirring is evaporated, finally, after being evaporated
Second solution be put into sintering furnace, at 650 DEG C, be sintered 7h, obtain manganese silicate of lithium cladding nickle cobalt lithium manganate ternary
Material.
It is discharged using the 712 nickel-cobalt-manganese ternary material of cladded type and traditional 712 nickel-cobalt-manganese ternary materials of above-mentioned acquisition
Performance comparison, flash-over characteristic comparison diagram is similar to Example 1, the 712 nickel-cobalt-manganese ternary material of cladded type that the present invention obtains,
Under 2.75-4.3V and normal temperature condition, 1C charge 2C electric discharge when, specific discharge capacity reaches 173mAh/g, and traditional 712 nickel cobalt manganeses three
First material, at 2.75-4.3V and normal temperature condition, when 1C charging 2C discharges, specific discharge capacity only reaches 159mAh/g, it is seen then that
The cladding of manganese silicate of lithium significantly improves the theoretical specific capacity of material.
Embodiment 8
The embodiment of the present invention provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding, and chemical general formula is
Li1.12Ni0.7Co0.1Mn0.23Si0.03O2.12。
The embodiment of the present invention also provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding as described in above scheme
Preparation method, method are implemented by following steps:
Step 1, by Ni0.7Co0.1Mn0.2(OH)2Ternary precursor is uniformly mixed with lithium source, then under oxygen atmosphere
It is sintered 16h at 800 DEG C, finally pulverizes and sieves, obtains once sintered product LiNi0.7Co0.1Mn0.2O2；
Wherein, the mole and Ni of lithium source0.7Co0.1Mn0.2(OH)2In ternary precursor the sum of mole of nickel cobalt manganese it
Than for 1.00≤Li:(Ni+Co+Mn)≤1.10；
Wherein, the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate；
Step 2, lithium salts is dissolved in enough water, carries out primary stirring 1.2h, the first solution is obtained, then with per hour
It is 4:1:1 that Li:Si:Mn molar ratio in silica and manganese salt to solution, which is added, to first solution in the rate of 1.5mol/L,
Secondary agitation is carried out at 100 DEG C and is stood, and manganese silicate of lithium cladding solution is obtained；
Wherein, silica described in the step 2 is nanometer grade powder, and the manganese salt is nano-scale particle；
Wherein, lithium salts described in the step 2 be lithium hydroxide or lithium oxalate, the manganese salt be manganese carbonate, manganese oxalate or
One of manganese oxide；
Step 3, by the once sintered product LiNi0.7Co0.1Mn0.2O2Manganese silicate of lithium cladding solution after being added to dilution
It is interior, the second solution is obtained, the solid-liquid mass ratio of the second solution of control is 3:1~1:5, and then stirring is evaporated, finally, after being evaporated
Second solution be put into sintering furnace, at 650 DEG C, be sintered 7h, obtain manganese silicate of lithium cladding nickle cobalt lithium manganate ternary
Material.
It is discharged using the 712 nickel-cobalt-manganese ternary material of cladded type and traditional 712 nickel-cobalt-manganese ternary materials of above-mentioned acquisition
Performance comparison, flash-over characteristic comparison diagram is similar to Example 1, the 712 nickel-cobalt-manganese ternary material of cladded type that the present invention obtains,
Under 2.75-4.3V and normal temperature condition, 1C charge 2C electric discharge when, specific discharge capacity reaches 171mAh/g, and traditional 712 nickel cobalt manganeses three
First material, at 2.75-4.3V and normal temperature condition, when 1C charging 2C discharges, specific discharge capacity only reaches 159mAh/g, it is seen then that
The cladding of manganese silicate of lithium significantly improves the theoretical specific capacity of material.
Embodiment 9
The embodiment of the present invention provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding, and chemical general formula is
Li1.16Ni0.7Co0.1Mn0.24Si0.04O2.16。
The embodiment of the present invention also provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding as described in above scheme
Preparation method, method are implemented by following steps:
Step 1, by Ni0.7Co0.1Mn0.2(OH)2Ternary precursor is uniformly mixed with lithium source, then under oxygen atmosphere
It is sintered 16h at 800 DEG C, finally pulverizes and sieves, obtains once sintered product LiNi0.7Co0.1Mn0.2O2；
Wherein, the mole and Ni of lithium source0.7Co0.1Mn0.2(OH)2In ternary precursor the sum of mole of nickel cobalt manganese it
Than for 1.00≤Li:(Ni+Co+Mn)≤1.10；
Wherein, the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate；
Step 2, lithium salts is dissolved in enough water, carries out primary stirring 2h, the first solution is obtained, then with per hour
It is 4:1:1 that Li:Si:Mn molar ratio in silica and manganese salt to solution, which is added, to first solution in the rate of 1.5mol/L,
Secondary agitation is carried out at 150 DEG C and is stood, and manganese silicate of lithium cladding solution is obtained；
Wherein, silica described in the step 2 is nanometer grade powder, and the manganese salt is nano-scale particle；
Wherein, lithium salts described in the step 2 be lithium hydroxide or lithium oxalate, the manganese salt be manganese carbonate, manganese oxalate or
One of manganese oxide；
Step 3, by the once sintered product LiNi0.7Co0.1Mn0.2O2Manganese silicate of lithium cladding solution after being added to dilution
It is interior, the second solution is obtained, the solid-liquid mass ratio of the second solution of control is 3:1~1:5, and then stirring is evaporated, finally, after being evaporated
Second solution be put into sintering furnace, at 650 DEG C, be sintered 7h, obtain manganese silicate of lithium cladding nickle cobalt lithium manganate ternary
Material.
It is discharged using the 712 nickel-cobalt-manganese ternary material of cladded type and traditional 712 nickel-cobalt-manganese ternary materials of above-mentioned acquisition
Performance comparison, flash-over characteristic comparison diagram is similar to Example 1, the 712 nickel-cobalt-manganese ternary material of cladded type that the present invention obtains,
Under 2.75-4.3V and normal temperature condition, 1C charge 2C electric discharge when, specific discharge capacity reaches 172mAh/g, and traditional 712 nickel cobalt manganeses three
First material, at 2.75-4.3V and normal temperature condition, when 1C charging 2C discharges, specific discharge capacity only reaches 159mAh/g, it is seen then that
The cladding of manganese silicate of lithium significantly improves the theoretical specific capacity of material.
Embodiment 10
The embodiment of the present invention provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding, and chemical general formula is
Li1.2Ni0.7Co0.1Mn0.25Si0.05O2.2。
The embodiment of the present invention also provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding as described in above scheme
Preparation method, method are implemented by following steps:
Step 1, by Ni0.7Co0.1Mn0.2(OH)2Ternary precursor is uniformly mixed with lithium source, then under oxygen atmosphere
It is sintered 10~20h at 700~900 DEG C, finally pulverizes and sieves, obtains once sintered product LiNi0.7Co0.1Mn0.2O2；
Wherein, the mole and Ni of lithium source0.7Co0.1Mn0.2(OH)2In ternary precursor the sum of mole of nickel cobalt manganese it
Than for 1.00≤Li:(Ni+Co+Mn)≤1.10；
Wherein, the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate；
Step 2, lithium salts is dissolved in enough water, carries out primary stirring 1.8h, the first solution is obtained, then with per hour
It is 4:1:1 that Li:Si:Mn molar ratio in silica and manganese salt to solution, which is added, to first solution in the rate of 0.6mol/L,
Secondary agitation is carried out at 100 DEG C and is stood, and manganese silicate of lithium cladding solution is obtained；
Wherein, silica described in the step 2 is nanometer grade powder, and the manganese salt is nano-scale particle；
Wherein, lithium salts described in the step 2 be lithium hydroxide or lithium oxalate, the manganese salt be manganese carbonate, manganese oxalate or
One of manganese oxide；
Step 3, by the once sintered product LiNi0.7Co0.1Mn0.2O2Manganese silicate of lithium cladding solution after being added to dilution
It is interior, the second solution is obtained, the solid-liquid mass ratio of the second solution of control is 3:1~1:5, and then stirring is evaporated, finally, after being evaporated
Second solution be put into sintering furnace, at 500 DEG C, be sintered 10h, obtain manganese silicate of lithium cladding nickle cobalt lithium manganate ternary
Material.
It is discharged using the 712 nickel-cobalt-manganese ternary material of cladded type and traditional 712 nickel-cobalt-manganese ternary materials of above-mentioned acquisition
Performance comparison, flash-over characteristic comparison diagram is similar to Example 1, the 712 nickel-cobalt-manganese ternary material of cladded type that the present invention obtains,
Under 2.75-4.3V and normal temperature condition, 1C charge 2C electric discharge when, specific discharge capacity reaches 174mAh/g, and traditional 712 nickel cobalt manganeses three
First material, at 2.75-4.3V and normal temperature condition, when 1C charging 2C discharges, specific discharge capacity only reaches 159mAh/g, it is seen then that
The cladding of manganese silicate of lithium significantly improves the theoretical specific capacity of material.
Embodiment 11
The embodiment of the present invention provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding, and chemical general formula is
Li1.08Ni0.6Co0.2Mn0.22Si0.02O2.08。
The embodiment of the present invention also provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding as described in above scheme
Preparation method, method are implemented by following steps:
Step 1, by Ni0.6Co0.2Mn0.2(OH)2Ternary precursor is uniformly mixed with lithium source, then under oxygen atmosphere
It is sintered 10~20h at 700~900 DEG C, finally pulverizes and sieves, obtains once sintered product LiNi0.6Co0.2Mn0.2O2；
Wherein, the mole and Ni of lithium source0.6Co0.2Mn0.2(OH)2In ternary precursor the sum of mole of nickel cobalt manganese it
Than for 1.00≤Li:(Ni+Co+Mn)≤1.10；
Wherein, the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate；
Step 2, lithium salts is dissolved in enough water, carries out primary stirring 1.8h, the first solution is obtained, then with per hour
It is 4:1:1 that Li:Si:Mn molar ratio in silica and manganese salt to solution, which is added, to first solution in the rate of 0.6mol/L,
Secondary agitation is carried out at 100 DEG C and is stood, and manganese silicate of lithium cladding solution is obtained；
Wherein, silica described in the step 2 is nanometer grade powder, and the manganese salt is nano-scale particle；
Wherein, lithium salts described in the step 2 be lithium hydroxide or lithium oxalate, the manganese salt be manganese carbonate, manganese oxalate or
One of manganese oxide；
Step 3, by the once sintered product LiNi0.6Co0.2Mn0.2O2Manganese silicate of lithium cladding solution after being added to dilution
It is interior, the second solution is obtained, the solid-liquid mass ratio of the second solution of control is 3:1~1:5, and then stirring is evaporated, finally, after being evaporated
Second solution be put into sintering furnace, at 700 DEG C, be sintered 7h, obtain manganese silicate of lithium cladding nickle cobalt lithium manganate ternary
Material.
It is discharged using the 622 nickel-cobalt-manganese ternary material of cladded type and traditional 622 nickel-cobalt-manganese ternary materials of above-mentioned acquisition
Performance comparison, flash-over characteristic comparison diagram is similar to Example 1, the 622 nickel-cobalt-manganese ternary material of cladded type that the present invention obtains,
Under 2.75-4.3V and normal temperature condition, 1C charge 2C electric discharge when, specific discharge capacity reaches 174mAh/g, and traditional 622 nickel cobalt manganeses three
First material, at 2.75-4.3V and normal temperature condition, when 1C charging 2C discharges, specific discharge capacity only reaches 159mAh/g, it is seen then that
The cladding of manganese silicate of lithium significantly improves the theoretical specific capacity of material.
Embodiment 12
The embodiment of the present invention provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding, and chemical general formula is
Li1.12Ni0.7Co0.1Mn0.23Si0.03O2.12。
The embodiment of the present invention also provides a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding as described in above scheme
Preparation method, method are implemented by following steps:
Step 1, by Ni0.7Co0.1Mn0.2(OH)2Ternary precursor is uniformly mixed with lithium source, then under oxygen atmosphere
It is sintered 10~20h at 700~900 DEG C, finally pulverizes and sieves, obtains once sintered product LiNi0.7Co0.2Mn0.1O2；
Wherein, the mole and Ni of lithium source0.7Co0.1Mn0.2(OH)2In ternary precursor the sum of mole of nickel cobalt manganese it
Than for 1.00≤Li:(Ni+Co+Mn)≤1.10；
Wherein, the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate；
Step 2, lithium salts is dissolved in enough water, carries out primary stirring 1.8h, the first solution is obtained, then with per hour
It is 4:1:1 that Li:Si:Mn molar ratio in silica and manganese salt to solution, which is added, to first solution in the rate of 0.6mol/L,
Secondary agitation is carried out at 100 DEG C and is stood, and manganese silicate of lithium cladding solution is obtained；
Wherein, silica described in the step 2 is nanometer grade powder, and the manganese salt is nano-scale particle；
Wherein, lithium salts described in the step 2 be lithium hydroxide or lithium oxalate, the manganese salt be manganese carbonate, manganese oxalate or
One of manganese oxide；
Step 3, by the once sintered product LiNi0.7Co0.1Mn0.2O2Manganese silicate of lithium cladding solution after being added to dilution
It is interior, the second solution is obtained, the solid-liquid mass ratio of the second solution of control is 3:1~1:5, and then stirring is evaporated, finally, after being evaporated
Second solution be put into sintering furnace, at 800 DEG C, be sintered 5h, obtain manganese silicate of lithium cladding nickle cobalt lithium manganate ternary
Material.
It is discharged using the 712 nickel-cobalt-manganese ternary material of cladded type and traditional 712 nickel-cobalt-manganese ternary materials of above-mentioned acquisition
Performance comparison, flash-over characteristic comparison diagram is similar to Example 1, the 712 nickel-cobalt-manganese ternary material of cladded type that the present invention obtains,
Under 2.75-4.3V and normal temperature condition, 1C charge 2C electric discharge when, specific discharge capacity reaches 172mAh/g, and traditional 712 nickel cobalt manganeses three
First material, at 2.75-4.3V and normal temperature condition, when 1C charging 2C discharges, specific discharge capacity only reaches 159mAh/g, it is seen then that
The cladding of manganese silicate of lithium significantly improves the theoretical specific capacity of material.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.
Claims (10)
1. a kind of nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding, which is characterized in that its chemical general formula is Li(1+4n)
NixCoyMn(1-x-y+n)SinO2+4n, wherein 0.6≤x≤0.7,0.1≤y≤0.2,0≤n≤0.05.
2. a kind of preparation method of the nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding as described in claim 1, which is characterized in that
Its method is implemented by following steps:
Step 1, by NixCoyMn(1-x-y)(OH)2Ternary precursor and lithium source according to lithium source mole and NixCoyMn(1-x-y)
(OH)2The ratio between the sum of mole of nickel cobalt manganese is 1.00≤Li:(Ni+Co+Mn in ternary precursor)≤1.10 uniformly mixing, so
It is sintered under oxygen atmosphere, finally pulverizes and sieves afterwards, obtain once sintered product LiNixCoyMn(1-x-y)O2；
Step 2, lithium salts is dissolved in enough water, is once stirred, obtain the first solution, be then added two to first solution
Li:Si:Mn molar ratio is 4:1:1 in silica and manganese salt to solution, carries out secondary agitation and stands, and obtains manganese silicate of lithium cladding
Solution；
Step 3, by the once sintered product LiNixCoyMn(1-x-y)O2It is added in manganese silicate of lithium cladding solution, it is molten to obtain second
Second solution is sintered by liquid, obtains the cobalt nickel lithium manganate ternary material of manganese silicate of lithium cladding.
3. a kind of preparation method of the nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding according to claim 2, feature exist
In lithium source described in the step 1 is at least one of lithium carbonate, lithium hydroxide or lithium oxalate.
4. a kind of preparation method of the nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding according to claim 3, feature exist
In sintering temperature is 700~900 DEG C in the step 1, and sintering time is 10~20h.
5. a kind of preparation side of the nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding according to claim 2-4 any one
Method, which is characterized in that the addition rate of silica described in the step 2 and manganese salt is 0.1~1.0mol/L per hour.
6. a kind of preparation method of the nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding according to claim 5, feature exist
In, silica described in the step 2 is nanometer grade powder, and the particle size range of the SiO 2 powder is 50~300nm,
The manganese salt is nano-scale particle, and the particle size range of the manganese salt particle is 50~1000nm.
7. a kind of preparation method of the nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding according to claim 6, feature exist
In lithium salts described in the step 2 is lithium hydroxide or lithium oxalate, and the manganese salt is in manganese carbonate, manganese oxalate or manganese oxide
It is a kind of.
8. a kind of preparation method of the nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding according to claim 7, feature exist
In the time once stirred of the step 2 is 1~2h, and the whipping temp of the secondary agitation is 50~150 DEG C.
9. a kind of preparation method of the nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding according to claim 8, feature exist
In the solid-liquid mass ratio of the second solution described in the step 3 is 3:1~1:5.
10. a kind of preparation method of the nickel-cobalt-manganese ternary material of manganese silicate of lithium cladding according to claim 9, feature exist
In sintering temperature is 500~800 DEG C in the step 3, and sintering time is 5~10h.
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Cited By (2)
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| CN112864363A (en) * | 2021-01-11 | 2021-05-28 | 宁德新能源科技有限公司 | Positive electrode material, electrochemical device, and electronic device |
| CN113023790A (en) * | 2021-02-26 | 2021-06-25 | 蜂巢能源科技有限公司 | Cathode material and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306765A (en) * | 2011-08-18 | 2012-01-04 | 合肥国轩高科动力能源有限公司 | Preparation method of nickel-manganese-cobalt lithium ion cathode material |
| CN103107337A (en) * | 2012-04-01 | 2013-05-15 | 湖南大学 | Method for improving cycling stability of lithium ion battery anode material |
| CN104124449A (en) * | 2014-08-04 | 2014-10-29 | 天津巴莫科技股份有限公司 | High-energy density nickel-series composite positive electrode material for lithium ion battery and preparation method of high-energy density nickel-series composite positive electrode material |
| CN104362334A (en) * | 2014-11-26 | 2015-02-18 | 中国科学院大学 | Preparation method of lithium metasilicate coated lithium-enriched laminar positive electrode material of lithium ion battery |
| CN104752685A (en) * | 2013-12-30 | 2015-07-01 | 北京当升材料科技股份有限公司 | Lithium ion batteries cathode material and preparation method thereof |
| CN107302087A (en) * | 2017-07-27 | 2017-10-27 | 格林美（无锡）能源材料有限公司 | A kind of lithium battery nickle cobalt lithium manganate tertiary cathode material and preparation method thereof |
| CN107331858A (en) * | 2017-06-23 | 2017-11-07 | 海南大学 | A kind of lithium ion battery tertiary cathode gradient distributed material presoma and its application |
-
2017
- 2017-12-25 CN CN201711424783.6A patent/CN109962217B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306765A (en) * | 2011-08-18 | 2012-01-04 | 合肥国轩高科动力能源有限公司 | Preparation method of nickel-manganese-cobalt lithium ion cathode material |
| CN103107337A (en) * | 2012-04-01 | 2013-05-15 | 湖南大学 | Method for improving cycling stability of lithium ion battery anode material |
| CN104752685A (en) * | 2013-12-30 | 2015-07-01 | 北京当升材料科技股份有限公司 | Lithium ion batteries cathode material and preparation method thereof |
| CN104124449A (en) * | 2014-08-04 | 2014-10-29 | 天津巴莫科技股份有限公司 | High-energy density nickel-series composite positive electrode material for lithium ion battery and preparation method of high-energy density nickel-series composite positive electrode material |
| CN104362334A (en) * | 2014-11-26 | 2015-02-18 | 中国科学院大学 | Preparation method of lithium metasilicate coated lithium-enriched laminar positive electrode material of lithium ion battery |
| CN107331858A (en) * | 2017-06-23 | 2017-11-07 | 海南大学 | A kind of lithium ion battery tertiary cathode gradient distributed material presoma and its application |
| CN107302087A (en) * | 2017-07-27 | 2017-10-27 | 格林美（无锡）能源材料有限公司 | A kind of lithium battery nickle cobalt lithium manganate tertiary cathode material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112864363A (en) * | 2021-01-11 | 2021-05-28 | 宁德新能源科技有限公司 | Positive electrode material, electrochemical device, and electronic device |
| CN112864363B (en) * | 2021-01-11 | 2022-07-01 | 宁德新能源科技有限公司 | Positive electrode material, electrochemical device, and electronic device |
| CN113023790A (en) * | 2021-02-26 | 2021-06-25 | 蜂巢能源科技有限公司 | Cathode material and preparation method and application thereof |
| CN113023790B (en) * | 2021-02-26 | 2023-06-16 | 蜂巢能源科技有限公司 | Positive electrode material and preparation method and application thereof |
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