CN105680025A - Lithium battery cathode material and preparation method thereof as well as lithium battery - Google Patents
Lithium battery cathode material and preparation method thereof as well as lithium battery Download PDFInfo
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- CN105680025A CN105680025A CN201610250000.6A CN201610250000A CN105680025A CN 105680025 A CN105680025 A CN 105680025A CN 201610250000 A CN201610250000 A CN 201610250000A CN 105680025 A CN105680025 A CN 105680025A
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Abstract
The application relates to a lithium battery cathode material. The lithium battery cathode material is spinel lithium nickel manganese oxide; the surface of spinel lithium nickel manganese oxide is coated with a coating; the coating comprises LiaBbOc and LiMnBO3; the structural formula of the spinel lithium nickel manganese oxide is LiM(x+y)Ni(0.5-x)Mn(1.5-y)O4, wherein the M is selected from at least one of Co, Al, Cr, Fe, Mg, Zr or Ti, the x is not less than 0 and is less than 0.2, and the y is not less than 0 and is less than 0.2; the LiaBbOc is specifically at least one of LiBO2, LiB3O5,LiB5O8, LiB7O11, Li2B4O7, Li3BO3, Li3B5O9, Li3B7O12, Li4B2O5 or Li4B6O11. The spinel lithium nickel manganese oxide and compounds of boron are mixed and sintered, so that the circling stability of the spinel lithium nickel manganese oxide is improved and the dissolution of manganese of the spinel lithium nickel manganese oxide in an electrolytic solution is restrained. An improved process is suitable for all spinel lithium nickel manganese oxide cathode materials and is simple and feasible, the preparation costs are low, the reproducibility is great, and the process is convenient for large-scale industrial production.
Description
Technical field
The application relates to technical field of lithium ion, is specifically related to a kind of anode material of lithium battery and preparation method thereof and lithium battery.
Background technology
Relative to secondary cells such as traditional lead-acid battery, Ni-MH batteries, lithium ion battery has that energy density is high, output voltage high, self discharge is low, memory-less effect and advantages of environment protection and be widely used and exploitation. The performance of power and energy storage lithium ion battery critical material is the final deciding factor of battery performance, and the research of positive electrode is always up the focus that scientist pays close attention to. LiCoO2、LiMnO4、LiFePO4、LiNixCoyMn1-x-yO2Studied widely Deng positive electrode. But there is the defects such as specific energy density is low, cost is high, poor stability in the lithium-ion battery system that these positive electrodes assemble, it is difficult to meets the electric motor car requirement to energy-storage battery.
Spinel nickel manganate cathode material for lithium, due to advantages such as its high rate performance are excellent, running voltage is high, with low cost, is always up the study hotspot of anode material for lithium-ion batteries. But the shortcomings such as spinel nickel manganate cathode material for lithium surface texture is unstable, manganese metal dissolution in cyclic process seriously inhibit the large-scale application of spinel nickel manganate cathode material for lithium.
In order to develop the spinel nickel manganate cathode material for lithium of excellent performance, meeting the electric motor car requirement to battery high rate performance, researcher has been researched and developed and has been disclosed multiple technologies means spinel nickel manganate cathode material for lithium is modified. As,
One of method of modifying: obtained the nickel ion doped material of aluminium hydroxide cladding by liquid phase coating, then inserting in Muffle furnace 300～450 DEG C and be thermally treated resulting in the nickel lithium manganate cathode material that alumina-coated is modified, the more uncoated material of modified nickel lithium manganate cathode material improves about 10%.
Method of modifying two: adopt sol-gel process to combine with solid phase method, so that at LiNi0.5Mn1.5The Li of O4 material cladding2TiO3It is evenly distributed, having good uniformity of the final positive electrode prepared so that the positive electrode prepared has good cycle performance and high rate performance.
Method of modifying three: by adding microwave susceptor zirconium oxide in precursor preparation process, promote reaction mass effectively to absorb microwave and be rapidly heated to reaction temperature 700-950 DEG C, the microwave firing time of notable shortening product was to 1-10 minute;While at high temperature nickel ion doped material burns till, zirconium oxide and Li source are reacted at nickel ion doped Surface Creation lithium ion conductor Li2ZrO3Clad, is obviously improved cycle performance and the high rate performance of product.
There is technique relative complex in above method, make it difficult to carry out industrialized production, solve but without corresponding method simultaneously for manganese metal dissolution, therefore, need the method for modifying finding a kind of simple spinel nickel manganate cathode material for lithium at present badly, make spinel nickel manganate cathode material for lithium have higher cyclical stability, and its manganese metal dissolution in the electrolytic solution can be suppressed, it is thus possible to meet the requirement of electrokinetic cell.
Summary of the invention
The application aims to overcome that problem of the prior art, it is provided that the spinel nickel manganate cathode material for lithium of a kind of surface modification and preparation method, and this material surface Stability Analysis of Structures, good cycling stability, and in cyclic process, manganese metal is not easy dissolution.
The concrete technical scheme of the application is:
A kind of anode material of lithium battery, described anode material of lithium battery is the spinel nickel LiMn2O4 that Surface coating has clad, comprises Li in described cladaBbOcAnd LiMnBO3。
Preferably, the structural formula of described spinel nickel LiMn2O4 is LiMx+yNi0.5-xMn1.5-yO4, wherein, M at least one in Co, Al, Cr, Fe, Mg, Zr or Ti, 0≤x < 0.2,0≤y < 0.2; Preferably, 0 < x+y < 0.2.
Preferably, described LiaBbOcIt is specially LiBO2、LiB3O5、LiB5O8、LiB7O11、Li2B4O7、Li3BO3、Li3B5O9、Li3B7O12、Li4B2O5Or Li4B6O11In at least one; It is more preferably LiBO2。
Preferably, wherein said LiaBbOcAnd LiMnBO3The ratio of amount of substance be 1:0.5～4.
Preferably, described clad accounts for the percentage ratio of described spinel nickel LiMn2O4 quality for more than zero and less than 3%.
Preferably, the thickness of described clad is 1～10nm.
The preparation method that the application further relates to front arbitrary described anode material of lithium battery, comprises the following steps:
(1) by spinel nickel LiMn2O4 raw material and boron source, lithium source Homogeneous phase mixing;
(2) mixed sintering under oxygen-containing atmosphere environment, prepares described anode material of lithium battery.
Preferably, in described step (1), described boron source is at least one in diboron trioxide, boric acid, Lithium biborate; Described lithium source is at least one in Lithium hydrate, lithium carbonate, Lithium biborate.
Preferably, the median particle diameter D50 of described spinel nickel LiMn2O4 raw material is 3 μm～15 μm, and the median particle diameter D50 of described boron source is 10nm～500nm, and the median particle diameter D50 in described lithium source is 0.1 μm～5 μm.
Preferably, the addition of described boron source is the 0.1～10% of described spinel nickel LiMn2O4 feed molar number; The 0%～400% of the molal quantity that addition is described boron source in described lithium source.
Preferably, described oxygen-containing atmosphere is oxygen or air, and gas flow rate is 100～5000ml/min; The heating rate of described mixed sintering is 1～10 DEG C/min, mixed sintering 3～8h at 400～800 DEG C.
The application further relates to a kind of lithium battery, and including anode pole piece, cathode pole piece, the barrier film being arranged at intervals between described anode pole piece and cathode pole piece and electrolyte, described anode pole piece contains front arbitrary described anode material of lithium battery.
The technical scheme that the application provides can reach following beneficial effect:
With the compound mixed sintering of spinel nickel LiMn2O4 Yu boron, not only increase the cyclical stability of spinel nickel LiMn2O4, and suppress the manganese dissolution in the electrolytic solution of spinel nickel LiMn2O4. Its modified technique is applicable to all spinel nickel manganate cathode material for lithium, simple, low cost of manufacture, favorable reproducibility, it is simple to large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is spinel nickel manganate cathode material for lithium and the comparative example 1 anode material of lithium battery LiNi of embodiment 1 preparation0.5Mn1.5O4XRD figure;
Fig. 2 is the anode material of lithium battery LiNi without sintering processes0.5Mn1.5O4SEM figure;
Fig. 3 is the SEM figure of the anode material of lithium battery that embodiment 1 prepares;
Fig. 4 is comparative example 1 positive electrode LiNi0.5Mn1.5O4Stable circulation linearity curve with the anode material of lithium battery that embodiment 1～2 prepares.
Detailed description of the invention
For making the purpose of the application, technical scheme and advantage clearly, below in conjunction with the embodiment of the present application and accompanying drawing, the technical scheme of the application is clearly and completely described, it is clear that, described embodiment is some embodiments of the present application, rather than whole embodiments. The technical scheme provided based on the application and given embodiment, the every other embodiment that those skilled in the art obtain under not making creative work premise, broadly fall into the scope of the application protection.
A kind of anode material of lithium battery that the application relates to, is the Surface coating spinel nickel LiMn2O4 that has one layer of clad, namely at one layer of clad of Surface coating of spinel nickel LiMn2O4; Clad comprises LiaBbOcAnd LiMnBO3。
Relative to independent LiaBbOcAnd conventional oxide, LiaBbOcAnd LiMnBO3Have the advantage that 1) LiMnBO3There is stable three-dimensional crystalline structure, and can be Li+Embedding/deintercalation more broad diffusion admittance is provided; 2) the manganese dissolution of spinel nickel LiMn2O4, the mainly Mn on surface3+It is dissolved in electrolyte, and migrates to negative plate SEI film, through Surface L iaBbOcAnd LiMnBO3Cladding, LiMnBO3Stabilize the manganese element on spinel nickel LiMn2O4 surface, make the Mn on surface be in stable valence state, decrease manganese dissolving in the electrolytic solution; 3) make positive electrode and electrolyte keep apart by Surface coating simultaneously, when in charge and discharge process, voltage is up to about 5V, the electrolyte of electrode surface oxidized decomposition will not be deposited on electrode surface, and reducing electrolyte in charge and discharge process affects the dissolving of positive electrode, erosion etc.
It is also preferred that the left the structural formula of spinel nickel LiMn2O4 is LiMx+yNi0.5-xMn1.5-yO4, wherein, M is at least one in Co, Al, Cr, Fe, Mg, Zr or Ti, 0≤x < 0.2,0≤y < 0.2; Preferably 0 < x+y < 0.2, more preferably 0 < x+y < 0.1.
As a kind of improvement of the application, a, b, c are integer, and 1≤a≤4,1≤b≤7,2≤c≤12, a+3b=2c, i.e. described LiaBbOcIt is specially LiBO2、LiB3O5、LiB5O8、LiB7O11、Li2B4O7、Li3BO3、Li3B5O9、Li3B7O12、Li4B2O5Or Li4B6O11In at least one; It is preferably LiBO2。
As a kind of improvement of the application, clad accounts for the percentage ratio of stratum nucleare spinel nickel LiMn2O4 quality for more than zero and less than 3%; Li in cladaBbOcAnd LiMnBO3The ratio of amount of substance be 1:0.5～4; The thickness of clad is 1～10nm.
As a kind of improvement of the application, clad is by LiaBbOcWith LiMnBO3Composition, clad accounts for stratum nucleare spinel nickel LiMn2O4 mass ratio less than 3%, wherein LiaBbOcAnd LiMnBO3The ratio of amount of substance be 1:0.5～4; The thickness of clad is 1～10nm.
For clad, wherein LiaBbOcThe too high storage aerogenesis that can increase positive electrode of ratio, LiMnBO3The too high D.C. resistance (DCR) that can increase battery core of ratio; Clad is too thin simultaneously, DeGrain; Clad is too thick, can increase the polarization in positive electrode charge and discharge process.
The preparation method that the application further relates to above-mentioned anode material of lithium battery, comprises the following steps:
(1) by spinel nickel LiMn2O4 raw material and boron source, lithium source Homogeneous phase mixing;
(2) mixed sintering under oxygen-containing atmosphere environment, prepares anode material of lithium battery.
Boron source, lithium source are formed in mixed sintering process with the manganese of instability in spinel nickel LiMn2O4 raw material and comprise LiaBbOcAnd LiMnBO3Clad so that manganese unstable in spinel nickel LiMn2O4 raw material occurs transfer stable existence in clad, thus suppressing the manganese dissolution in the electrolytic solution of spinel nickel LiMn2O4; Sintering process spinel nickel LiMn2O4 also forms boron lithium composite xoide Li with boron source and lithium source simultaneously in cladaBbOc, the cyclical stability of spinel nickel LiMn2O4 can be effectively improved. The modified technique of this solid-phase sintering can be applicable to all spinel nickel manganate cathode material for lithium, simple, low cost of manufacture, favorable reproducibility, it is simple to large-scale industrial production.
As a kind of improvement of the application, in step (1), boron source is at least one in diboron trioxide, boric acid, Lithium biborate; Lithium source is at least one in Lithium hydrate, lithium carbonate, Lithium biborate.
It is also preferred that the left the addition of described boron source is described spinel nickel LiMn2O4 feed molar number 0.1～10%; The 0%～400% of the molal quantity that addition is described boron source in described lithium source. Wherein the situation of 0% is when containing elemental lithium in boron source simultaneously, and at this moment boron source can provide boron and lithium simultaneously, therefore without additionally adding other lithium source, as when boron source is Lithium biborate, Lithium biborate functions simultaneously as boron source and lithium source.
As a kind of improvement of the application, the median particle diameter D50 of spinel nickel LiMn2O4 raw material is 3 μm～15 μm, and the median particle diameter D50 of boron source is 10nm～500nm, and the median particle diameter D50 in lithium source is 0.1 μm～5 μm.
As a kind of improvement of the application, mixed uniformly method is ball milling, grinding or magnetic agitation etc., uses ball milling, grinding or magnetic agitation can be effectively improved mixing homogeneity, is conducive to improving transformation efficiency.
As a kind of improvement of the application, oxygen-containing atmosphere is oxygen or air, and gas flow rate is 100～5000ml/min; The heating rate of mixed sintering is 1～10 DEG C/min, and at 400～800 DEG C, the mixed sintering time is 3～8h; Use certain oxygen-containing atmosphere, can effectively oxygenating, simultaneously too high or too low for temperature coating thickness all can be caused too thick or too thin.
The application further relates to a kind of lithium battery positive pole active substance, containing aforesaid anode material of lithium battery. That is, in the active substance of lithium ion battery anode that the application relates to, except the anode material of lithium battery of the aforementioned offer of the application, however not excluded that can as the composition of active substance of lithium ion battery anode possibly together with other.
The application further relates to a kind of lithium battery anode piece, and including the positive electrode active material layer on collector and distribution collector, positive electrode active material layer comprises aforesaid lithium battery positive pole active substance, namely comprises aforesaid anode material of lithium battery in positive electrode active material layer. Possibly together with conductive agent and binding agent in general positive electrode active material layer, conductive agent and binding agent in the positive electrode active material layer that the application relates to can use existing conductive agent and binding agent; Such as, the conductive agent such as graphite, CNT; Such as, the binding agent such as PVDF.
The application further relates to a kind of lithium ion battery, including anode pole piece, cathode pole piece, the barrier film being arranged at intervals between anode pole piece and cathode pole piece and electrolyte, anode pole piece is aforesaid anode slice of lithium ion battery, and namely anode pole piece contains aforesaid anode material of lithium battery.
Embodiment 1～6 and comparative example 1～3: take spinel nickel LiMn2O4 raw material, boron source, lithium source by certain thing mass ratio, mix homogeneously, it is subsequently placed in oxygen atmosphere, set gas flow rate as 1000ml/min, 5 DEG C/min of heating rate, sinter 5h at 450 DEG C, prepare the spinel nickel manganate cathode material for lithium that surface boron is modified; Wherein comparative example 1 is situation about not being sintered; Preparation process relevant parameter is specifically as shown in table 1.
Table 1 embodiment 1～6 and comparative example 1～3 prepare modified spinelle nickel lithium manganate cathode material relevant parameter
Embodiment 7～9 and comparative example 4～7: the spinel nickel manganate cathode material for lithium that preparation surface boron is modified: with raw material and the proportioning of embodiment 6, take spinel nickel LiMn2O4 LiAl0.1Ni0.5Mn1.4O4(D50 is 10 μm), Li3BO3(D50 is 200nm) grinds Homogeneous phase mixing, then carries out solid-phase sintering reaction under different sintering conditions, and actual conditions is as shown in table 2.
Table 2 embodiment 7～9 and comparative example 4～7 reaction condition parameter list
The spinel nickel manganate cathode material for lithium of Example 1 preparation and LiNi0.5Mn1.5O4Respectively at X ' PertPROX x ray diffractometer x, step-scan, 0.02 degrees second, often 1 second time of staying of step, under 2 θ sweep limits 10～80 ° conditions, carry out X-ray powder diffraction experiment, the XRD figure that obtains spectrum is as it is shown in figure 1, with LiBO under condition2And LiMnBO3Scanning result be also compiled in Fig. 1; As can be seen from the figure product X RD collection of illustrative plates contains and Li1Ni0.5Mn1.5O4、LiBO2And LiMnBO3Identical characteristic peak, thus may determine that embodiment 1 solid-phase sintering defines LiBO2And LiMnBO3;
Raw material Li Ni0.5Mn1.5O4Electron scanning micrograph (× 50000) as shown in Figure 2; The electron scanning micrograph of the anode material of lithium battery that embodiment 1 prepares is (× 30000) as shown in Figure 3. Comparison diagram 2 and Fig. 3 are it can be seen that sintered prepared spinel nickel manganate cathode material for lithium has uniformly been coated with layer of substance, and compose according to above-mentioned XRD figure, and namely this clad material is LiBO2And LiMnBO3, thus further demonstrating by solid sintering technology enough in one layer of uniform LiBO of spinel nickel manganate cathode material for lithium surface formation2And LiMnBO3Clad.
Adopt XRD diffraction conditions same as described above, embodiment 1～9 sintered product is carried out X-ray diffraction analysis, after acetonideexample 1～9 spinel nickel manganate cathode material for lithium is sintered, all define one layer of clad on surface; The product that embodiment 1～9 and comparative example 1～7 obtain carrying out X-ray diffraction, and carries out qualitative and quantitative analysis according to the XRD figure spectrum obtained, result is summarized in table 3.
Wherein, quantitative analysis method is: clad LiaBbOcAnd LiMnBO3XRD highest peak integral area and the ratio of the XRD highest peak integral area of stratum nucleare spinel nickel LiMn2O4, obtain clad and account for stratum nucleare mol ratio, thus obtaining mass percent.
The positive electrode parameter list that table 3 embodiment 1～9 and comparative example 1～7 prepare
Cyclical stability is tested:
The anode material of lithium battery that Example 1～9 and comparative example 1～7 prepare makes and helps battery, is circulated stability test under the same conditions.
Method of testing is: under 25 DEG C of conditions, is charged to 4.9V with 0.5C (C is for battery capacity) multiplying power, discharges under 1.0C multiplying power, and after record circulation 200 circle, the capability retention of battery core, test result is as shown in table 4.
The cycle-index of embodiment 1～2 and comparative example 1 material is with the invariance curve of capability retention as indicated at 4.It can be seen that the capability retention of material all reduces with the increase of cycle-index; The spinel nickel manganate cathode material for lithium of the surface modification that employing the embodiment of the present application prepares, is formed without containing LiBO compared to comparative example 12/LiMnBO3The spinel nickel LiMn2O4 of clad has better cyclical stability.
Mn dissolution is tested:
The anode material of lithium battery that Example 1～9 and comparative example 1～7 prepare, carries out Mn dissolution test under the same conditions.
Method of testing is: be placed on by material in electrolyte (FEC:DMC=3:7), the mass ratio simultaneously making spinel nickel LiMn2O4 therein and electrolyte is 1:10, under 25 DEG C of conditions, completely cut off air place 48h, take the supernatant in electrolyte, utilize the content of Mn element in inductively coupled plasma spectrum generator test electrolyte, carry out Mn dissolution test, the test result obtained is as indicated at 4, the anode material of lithium battery that visible employing the application condition prepares, Mn dissolution content is extremely low.
The test result of table 4 embodiment 1～9 and comparative example 1～7 positive electrode
From upper table it can also be seen that relative to uncoated material, the material circulation stability after the surface-modified formation clad of the application improves; Material nickel ion doped doping Al and Mg can be effectively improved the cyclical stability of material; LiBO2Relative to LiB3O5Show more excellent performance; And, temperature is too high and sintering time is oversize all can cause coating thickness too thick accordingly, reduces the cyclical stability of material.
, also find in experimentation, Li in clad meanwhileaBbOcThe too high storage aerogenesis that can increase positive electrode of ratio, LiMnBO3The too high D.C. resistance (DCR) that can increase battery core of ratio; Clad is too thin simultaneously, for improving the DeGrain of material; Clad is too thick, can increase the polarization in positive electrode charge and discharge process.
Although the application is with preferred embodiment openly as above; but it is not for limiting claim; any those skilled in the art are under the premise conceived without departing from the application; can making some possible variations and amendment, therefore the protection domain of the application should be as the criterion with the scope that the application claim defines.
Claims (10)
1. an anode material of lithium battery, it is characterised in that described anode material of lithium battery is the spinel nickel LiMn2O4 that Surface coating has clad, comprises Li in described cladaBbOcAnd LiMnBO3。
2. anode material of lithium battery according to claim 1, it is characterised in that the structural formula of described spinel nickel LiMn2O4 is LiMx+yNi0.5-xMn1.5-yO4, wherein, M at least one in Co, Al, Cr, Fe, Mg, Zr or Ti, 0≤x < 0.2,0≤y < 0.2; Preferably, 0 < x+y < 0.2.
3. anode material of lithium battery according to claim 1, it is characterised in that described LiaBbOcIt is specially LiBO2、LiB3O5、LiB5O8、LiB7O11、Li2B4O7、Li3BO3、Li3B5O9、Li3B7O12、Li4B2O5Or Li4B6O11In at least one; It is preferably LiBO2。
4. anode material of lithium battery according to claim 1, it is characterised in that described LiaBbOcAnd LiMnBO3The ratio of amount of substance be 1:0.5～4; Preferably, described clad accounts for the percentage ratio of described spinel nickel LiMn2O4 quality for more than zero and less than 3%; It is furthermore preferred that the thickness of described clad is 1～10nm.
5. a preparation method for the anode material of lithium battery according to Claims 1 to 4 any claim, comprises the following steps:
(1) by spinel nickel LiMn2O4 raw material and boron source, lithium source Homogeneous phase mixing;
(2) mixed sintering under oxygen-containing atmosphere environment, prepares described anode material of lithium battery.
6. preparation method according to claim 5, it is characterised in that in described step (1), described boron source is at least one in diboron trioxide, boric acid, Lithium biborate; Described lithium source is at least one in Lithium hydrate, lithium carbonate, Lithium biborate.
7. preparation method according to claim 6, it is characterized in that, in described step (1), the median particle diameter D50 of described spinel nickel LiMn2O4 raw material is 3 μm～15 μm, the median particle diameter D50 of described boron source is 10nm～500nm, and the median particle diameter D50 in described lithium source is 0.1 μm～5 μm.
8. preparation method according to claim 6, it is characterised in that the addition of described boron source is the 0.1～10% of described spinel nickel LiMn2O4 feed molar number; The 0%～400% of the molal quantity that addition is described boron source in described lithium source.
9. preparation method according to claim 5, it is characterised in that described oxygen-containing atmosphere is oxygen or air, gas flow rate is 100～5000ml/min; The heating rate of described mixed sintering is 1～10 DEG C/min, mixed sintering 3～8h at 400～800 DEG C.
10. a lithium battery, including anode pole piece, cathode pole piece, the barrier film being arranged at intervals between described anode pole piece and cathode pole piece and electrolyte, it is characterised in that described anode pole piece contains the arbitrary described anode material of lithium battery of Claims 1 to 4.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610250000.6A CN105680025B (en) | 2016-04-21 | 2016-04-21 | A kind of anode material of lithium battery and preparation method thereof and lithium battery |
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| CN201610250000.6A CN105680025B (en) | 2016-04-21 | 2016-04-21 | A kind of anode material of lithium battery and preparation method thereof and lithium battery |
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| CN105680025A true CN105680025A (en) | 2016-06-15 |
| CN105680025B CN105680025B (en) | 2018-10-12 |
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Cited By (12)
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| CN107507976A (en) * | 2017-07-21 | 2017-12-22 | 中南大学 | Composite mixed manganate cathode material for lithium of a kind of lithium aluminium boron and preparation method thereof |
| CN108206278A (en) * | 2016-12-20 | 2018-06-26 | 宁德时代新能源科技股份有限公司 | Modified lithium ion battery positive electrode material, preparation method thereof and lithium ion battery |
| CN110121801A (en) * | 2016-12-22 | 2019-08-13 | 株式会社Posco | Positive electrode active materials and preparation method thereof and lithium secondary battery comprising it |
| CN112993219A (en) * | 2019-12-16 | 2021-06-18 | 济南圣泉集团股份有限公司 | Positive electrode material, battery positive electrode, battery and preparation method of lithium battery positive electrode material |
| WO2021156124A1 (en) * | 2020-02-07 | 2021-08-12 | Basf Se | Cathode active material and method for making such cathode active material |
| CN113991081A (en) * | 2021-10-27 | 2022-01-28 | 浙江大学 | Modified layered lithium-rich manganese oxide cathode material and application thereof |
| CN114039040A (en) * | 2021-10-29 | 2022-02-11 | 蜂巢能源科技有限公司 | Full battery and preparation method thereof |
| EP3896761A4 (en) * | 2019-03-22 | 2022-03-09 | Lg Energy Solution, Ltd. | Cathode active material particles for sulfide-based all-solid battery |
| CN114506877A (en) * | 2020-11-17 | 2022-05-17 | 松山湖材料实验室 | Method for preparing positive electrode active material, positive electrode, and lithium ion secondary battery |
| US11575116B2 (en) | 2019-03-22 | 2023-02-07 | Lg Energy Solution, Ltd. | Positive electrode active material particle for sulfide-based all-solid-state batteries |
| CN116425204A (en) * | 2023-04-28 | 2023-07-14 | 巴斯夫杉杉电池材料有限公司 | Spinel type lithium manganate, preparation method thereof and lithium ion battery |
| WO2024128833A1 (en) * | 2022-12-16 | 2024-06-20 | 포스코홀딩스 주식회사 | Cathode active material for all-solid-state battery, manufacturing method therefor, and all-solid-state battery including same |
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| CN108206278A (en) * | 2016-12-20 | 2018-06-26 | 宁德时代新能源科技股份有限公司 | Modified lithium ion battery positive electrode material, preparation method thereof and lithium ion battery |
| CN110121801A (en) * | 2016-12-22 | 2019-08-13 | 株式会社Posco | Positive electrode active materials and preparation method thereof and lithium secondary battery comprising it |
| EP3561919A4 (en) * | 2016-12-22 | 2020-01-08 | Posco | Cathode active material, method for preparing same, and lithium secondary battery comprising same |
| JP2020514970A (en) * | 2016-12-22 | 2020-05-21 | ポスコＰｏｓｃｏ | Positive electrode active material, method for producing the same, and lithium secondary battery including the same |
| CN107507976A (en) * | 2017-07-21 | 2017-12-22 | 中南大学 | Composite mixed manganate cathode material for lithium of a kind of lithium aluminium boron and preparation method thereof |
| EP3896761A4 (en) * | 2019-03-22 | 2022-03-09 | Lg Energy Solution, Ltd. | Cathode active material particles for sulfide-based all-solid battery |
| US11575116B2 (en) | 2019-03-22 | 2023-02-07 | Lg Energy Solution, Ltd. | Positive electrode active material particle for sulfide-based all-solid-state batteries |
| CN112993219A (en) * | 2019-12-16 | 2021-06-18 | 济南圣泉集团股份有限公司 | Positive electrode material, battery positive electrode, battery and preparation method of lithium battery positive electrode material |
| WO2021156124A1 (en) * | 2020-02-07 | 2021-08-12 | Basf Se | Cathode active material and method for making such cathode active material |
| CN114506877B (en) * | 2020-11-17 | 2023-12-15 | 松山湖材料实验室 | Preparation method of positive electrode active material, positive electrode and lithium ion secondary battery |
| CN114506877A (en) * | 2020-11-17 | 2022-05-17 | 松山湖材料实验室 | Method for preparing positive electrode active material, positive electrode, and lithium ion secondary battery |
| CN113991081A (en) * | 2021-10-27 | 2022-01-28 | 浙江大学 | Modified layered lithium-rich manganese oxide cathode material and application thereof |
| CN114039040A (en) * | 2021-10-29 | 2022-02-11 | 蜂巢能源科技有限公司 | Full battery and preparation method thereof |
| WO2024128833A1 (en) * | 2022-12-16 | 2024-06-20 | 포스코홀딩스 주식회사 | Cathode active material for all-solid-state battery, manufacturing method therefor, and all-solid-state battery including same |
| CN116425204A (en) * | 2023-04-28 | 2023-07-14 | 巴斯夫杉杉电池材料有限公司 | Spinel type lithium manganate, preparation method thereof and lithium ion battery |
| CN116425204B (en) * | 2023-04-28 | 2024-03-22 | 巴斯夫杉杉电池材料有限公司 | Spinel type lithium manganate, preparation method thereof and lithium ion battery |
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