Patent Application
20250112235
A lithium compound, a nickel-based cathode active material, a method for preparing lithium oxide, a method for preparing a nickel-based cathode active material, and a secondary battery using the same are disclosed.
Lithium secondary batteries have a high energy density, which is 1.5 to 2 times higher than that of Ni/Cd batteries, when compared at the same volume and thus are widely used as a power source for mobile phones, laptops, electric vehicles, and the like. Since the lithium secondary batteries as a main component determine performance of the portable products, a need for high performance batteries is emerged. Battery performance is required as high efficiency characteristics, stability at high temperatures, cycle-life, charge/discharge characteristics, etc.
In particular, as cells are coupled in parallel, over-discharge in the lithium secondary batteries may be magnified as an important factor.
Currently, lithium secondary batteries based on a lithium metal oxide as a cathode and carbon as an anode are used in most markets. In general, cycle-life efficiency of a cathode material based on the lithium metal oxide is higher than that of an anode material based on the carbon.
In such an environment, the more frequent over-discharges, the more side reactions occur at the anode, resulting in a short circuit of the cells coupled in parallel. In order to solve this problem, a method of increasing the efficiency of the anode or matching the efficiency of the cathode to that of the anode may be adopted, but there are many obstacles to increasing the efficiency of the anode. Accordingly, a lithium nickel oxide (Li2NiO2) with a rhombic Immm structure as a representative cathode additive for matching the efficiency of the cathode to that of the anode is being researched.
However, there is a drawback that lithium oxide, a precursor of the lithium nickel oxide, is expensive. In order to solve this problem, another lithium nickel oxide-manufacturing process of using lithium hydroxide, lithium carbonate, lithium nitrate, etc. as the precursor has been researched but faces difficulties in production according to processibility deterioration due to a reaction with a crucible used during the sintering at a high temperature and the manufacturing.
Specifically, over-lithiated transition metal oxide is synthesized in a method of mixing transition metal oxide of MOx (NiO, CoO, FeO, MnO, etc.) as a raw material with lithium oxide (Li2O) of a reaction equivalent or more and heat-treating the mixture.
When the transition metal oxide and the lithium oxide (Li2O) mixed to synthesize the over-lithiated transition metal oxide are not completely reacted, there may be problems of reducing irreversible capacity, reversible capacity, and reversible efficiency and shortening a cathode battery cycle-life in the electrochemical reaction of the over-lithiated transition metal oxide.
In addition, during the battery manufacturing process, there also may be problems such as slurry clogging and electrode coating defects due to solidification of the liquid electrode slurry.
After manufacturing a battery, there still may be problems of gas generation due to decomposition of an electrolyte solution, battery cycle-life decrease and explosion due to the battery swelling, high temperature stability deterioration, and the like.
There is no method of easily detecting the over-lithiated transition metal oxide synthesized by an incomplete reaction, but even when re-sintered, there is a problem of still not securing a complete reaction, and the lithium oxide (Li2O) may be more added thereto but supply an excessive amount of lithium, exacerbating the problems listed above.
Accordingly, since the particle size and shape of the over-lithiated transition metal oxide are determined by properties of the transition metal oxide, changing the properties of the transition metal oxide is limited.
Accordingly, in order to improve an incomplete reaction of the over-lithiated transition metal oxide, there are needs for improving a reactivity and miscibility of lithium oxide (Li2O) with the transition metal oxide.
In an embodiment of the present invention, in order to improve the degree of mixing with the transition metal oxide, the shape of the lithium oxide may be adjusted to a spherical shape.
In order to facilitate adsorption on the surface of the transition metal oxide during the mixing process, lithium oxide is composed of small primary particles of less than or equal to 5 μm. Lithium oxide composed of fine particles has a large specific surface area, resulting in high reactivity. More specifically, it may be composed of particles of less than or equal to 1 μm.
Fine primary particles are easily floated, resulting in poor process workability, large material loss, and aggregation of lithium oxide powders due to electrostatic force, resulting in low miscibility. Therefore, it is desirable that the fine primary particles are aggregated to constitute secondary particles having a size similar to that of the transition metal oxide.
Lithium oxide in the form of secondary particles may be pulverized during mixing with the transition metal oxide to be uniformly distributed on the surface of the transition metal oxide.
Impurities contained in lithium oxide may cause eutectic reaction with lithium oxide, lowering the dissolution temperature of lithium oxide, and ultimately increasing the reactivity of lithium oxide, and thus, there may be some positive effects within the permitted range.
This improved lithium oxide will be described in detail below.
An embodiment of the present invention provides a lithium compound including Li2O primary particles having an average particle diameter (D50) of less than or equal to 5 μm; and secondary particles composed of the primary particles. The lithium compound may be lithium oxide. Descriptions for the purposes and effects of the primary particles and secondary particles are the same as described above.
The secondary particles may have a spherical shape. Lithium oxide currently commercially available does not have a spherical shape and may have a particle composition of various shapes. It is possible to achieve improved reactivity with the transition metal oxide from a uniform spherical shape.
More specifically, the average particle diameter (D50) of the secondary particles may be 10 to 100 μm. Alternatively, the average particle diameter (D50) of the secondary particles may be 10 to 30 μm. This may be adjusted according to the size of the selected transition metal oxide.
Another embodiment of the present invention provides a nickel-based cathode active material derived from a lithium compound including primary Li2O particles having an average particle diameter (D50) of less than or equal to 5 μm and secondary particles composed of the primary particles; and a nickel raw material.
The cathode active material may be Li2NiO2, and Dmin may be greater than or equal to 5 μm.
The cathode active material may include a residual lithium compound of less than or equal to 2.5 wt % based on 100 wt % of the total weight. This is caused by the characteristics of the lithium raw material as described above. Due to the improved reactivity of lithium oxide in the form of secondary particles, residual lithium characteristics may be improved.
Specifically, it may be prepared in two steps of a wet reaction of lithium hydroxide raw materials and a high-temperature decomposition reaction in a low-oxygen atmosphere.
The schematic synthesis method of each step is as follows. In each process, it is desirable to maintain an inert atmosphere in order to prevent contamination by moisture and CO2 in the atmosphere and promote material conversion.
A theoretical reaction ratio between lithium hydroxide and hydrogen peroxide solution may be 2:1, but the ratio may be adjusted to improve the reaction yield. This will be described later.
As the raw material, lithium hydroxide monohydrate (LiOH—H2O), lithium hydroxide anhydride (LiOH), or lithium hydroxide polyhydride (LiOH-xH2O) may be used. In order to improve the reaction yield, it is desirable to use lithium hydroxide anhydride.
The hydrogen peroxide may be used as an aqueous solution (H2O2-zH2O, z is an integer of 0 or more). In order to improve the reaction yield, it is recommended to use pure hydrogen peroxide, but it is desirable to use an aqueous solution having a concentration of 35% for storage and safety reasons.
The particle size and shape of the Li2O2 intermediate material generated by controlling the shape of the reactor, the shape and dimension of the internal baffle and the impeller, the number of rotations of the impeller, the reactor temperature, etc. may be controlled. As the number of rotations of the impeller increases, the average sizes of the particles decrease, and spherical particles are formed.
As the reactor temperature is higher, the average size of the particles may be larger and the shape may be changed from spherical to amorphous.
The reaction time may be 1 minute or more after the raw materials is added, and about 30 to 60 minutes may be suitable.
Although it is not necessary to adjust the temperature of the reactor, it is desirable to adjust it within the range of 30 to 60° C. in order to control the reaction rate.
The solution and solids may be separated by sedimenting the prepared slurry, passing through a filter, or centrifugation. The recovered solution may be a lithium hydroxide aqueous solution in which an excess of lithium is dissolved, and may be used to prepare a lithium compound. The recovered Li2O2 solids may be dried on the surface of adsorbed water through vacuum drying.
The recovered solids are converted into Li2O2 at high temperature in an inert or vacuum atmosphere. The conversion temperature may be at 300° C. or higher, and desirably 400° C. to 600° C.
Nitrogen filling and vacuum packaging are desirable to prevent deterioration in the atmosphere.
In particular, there is a risk of being deteriorated into lithium hydroxide and lithium carbonate when it comes into contact with moisture in the atmosphere and CO2 at the same time.
Hereinafter, a preparing method according to an embodiment of the present invention is described in detail.
Another embodiment of the present invention provides a method for preparing lithium oxide that includes reacting hydrogen peroxide (H2O2) and lithium hydroxide (LiOH) to obtain over-lithiated oxide (Li2O2); and heat-treating the over-lithiated oxide to obtain lithium oxide (Li2O); wherein in the reacting of the hydrogen peroxide (H2O2) and lithium hydroxide (LiOH) to obtain a over-lithiated oxide (Li2O2), a mole ratio (Li/H2O2) of lithium of lithium hydroxide to hydrogen peroxide is 1.9 to 2.4.
In the reacting of hydrogen peroxide (H2O2) and lithium hydroxide (LiOH) to obtain over-lithiated oxide (Li2O2); the reaction temperature may be 40 to 60° C.
In the reacting of hydrogen peroxide (H2O2) and lithium hydroxide (LiOH) to obtain over-lithiated oxide (Li2O2); the reaction of hydrogen peroxide (H2O2) and lithium hydroxide (LiOH) may be accompanied by stirring at 500 rpm or more.
The heat-treating of the over-lithiated oxide to obtain lithium oxide (Li2O) may be performed at 400 to 600° C. in an inert atmosphere.
For conditions such as the mole ratio, reaction temperature, and stirring, the meanings of the ranges will be described in detail in examples and experimental examples described later.
Another embodiment of the present invention provides a method for preparing a nickel-based cathode active material includes reacting hydrogen peroxide (H2O2) and lithium hydroxide (LiOH) to obtain over-lithiated oxide (Li2O2); heat-treating the over-lithiated oxide to obtain lithium oxide (Li2O); and firing the lithium oxide and nickel raw material to obtain a nickel-based cathode active material, wherein in the reacting of the hydrogen peroxide (H2O2) and lithium hydroxide (LiOH) to obtain a over-lithiated oxide (Li2O2), a mole ratio (Li/H2O2) of lithium of lithium hydroxide to hydrogen peroxide is 1.9 to 2.4.
Another embodiment of the present invention provides a secondary battery that includes a cathode including a nickel-based cathode active material derived from a lithium compound including primary Li2O particles having an average particle diameter (D50) of less than or equal to 5 μm and secondary particles composed of the primary particles; and a nickel raw material; an anode including a anode active material; and an electrolyte between the cathode and the anode.
A conversion rate may increase during the synthesis of nickel-based lithium oxide compared with the conventional Li2O, which can lead to an increase in electrochemical capacity, a decrease in the residual lithium content, and an increase in material efficiency.
Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the present invention is not limited thereto and the present invention is defined by the scope of claims.
After introducing LH powder and H2O2, a stirring reaction was started, wherein the reaction time was 60 minutes.
The resultant was filtered with a vacuum-filtering device to recover the Li2O2 powder. The recovered powder was dried in a 130° C. vacuum oven for 3 hours. The powder was quantitatively analyzed in a Rietveld refinement method after the XRD measurement. (HighScore Plus Program made by Malvern Panalytical Ltd. was used)
Li2O2 acquisition yield=(Li2O2 acquisition amount)/(Li2O2 acquisition amount when the injected Li raw material is 100% converted), wherein a temperature is a predetermined temperature, and a measured temperature may be 2 to 3° C. lower than that.
Table 1 shows results with respect to purity of the synthesized Li2O2 powders.
Table 2 shows weights of the synthesized dry powders. The weights of the synthesized dry powders need to be compared with Li2O2 acquisition amounts when theoretically 100% converted. Since the obtained powders are not 100% Li2O2, simply a heavy weight is not good.
The results of Tables 1 and 2 may be used to calculate the Li2O2 acquisition yields, and the results are shown in Table 3. Specifically, the results of Table 3 were obtained by multiplying the results of Table 1 with the results of Table 2 and dividing the products by theoretical Li2O2 amounts.
At a low temperature, since LH was precipitated and not converted into Li2O2, Li2O2 purity was decreased. At a high temperature, H2O2 was decomposed, decreasing the Li2O2 purity.
When a Li/H2O2 ratio was low, a Li2O2 production yield was expected to decrease due to its high dissolution loss in H2O2. When the Li/H2O2 ratio was high, LH was precipitated, decreasing the Li2O2 purity.
An optimal ratio obtained therefrom is shown in Table 4.
Li2O2 was precipitated at 60° C. by controlling reaction time within various ranges as shown in Table 5 below. A specific method was the same as in Experiment 1.
At the 60° C., a reaction was completed within a short time of 10 minutes. After waiting for 60 minutes, the purity decreased. As the waiting time increased, the Li2O2 purity decreased. The reason is that LiOH increased according to decomposition of hydrogen peroxide. There was almost no difference in particle size and shape.
Table 6 shows the results of Experiment 2.
A shape change according to rpm of a reactor was examined. Li2O2 with purity of 98% or higher was synthesized regardless of rpm.
There was no shape change at greater than or equal to 500 rpm. The particles had a nonuniform size at 150 rpm.
When rpm was controlled to be greater than or equal to 500, desired effects were expected to be obtained.
Specifically, a co-precipitation reactor used for synthesizing a secondary battery cathode precursor was used to synthesize Li2O2. The reactor and an impeller had shapes shown in
In order to shorten the reaction time, a method of injecting the hydrogen peroxide solution was changed.
A quantitative injection was basically used, but in order to shorten the reaction time, the hydrogen peroxide solution was added manually and then added with a quantitative pump, followed by reacting them.
The results are shown in Table 7.
As a result of using the co-precipitation reactor, sphericity of particles was increased.
In addition, the higher rpm, the smaller D50 of secondary particles. (Comparison of a, b, and c)
When H2O2 was quantitatively slowly added, the particles became larger. (Comparison of d with e)
A reaction rate and rpm may be adjusted to control a particle size.
Li2O2 synthesized in Experiment 4 was converted into Li2O through a heat treatment at 420° C. for 3 hours under a nitrogen atmosphere. Converted components are shown in Table 8.
The results show that particle size and shape were affected by Li2O2.
Additionally, a furnace as shown in
10 g of Li2O2 was charged inside, and after removing the internal air with a vacuum pump for 30 minutes, the heat treatment was started while flowing N2. When the heat treatment was completed, powder was discharged and cooled down under a nitrogen atmosphere to be recovered.
During the heat treatment, a flow rate of the nitrogen varied from 1 L to 5 L per minute, but there was no difference depending on the flow rate.
Table 9 shows the heat treatment results.
As shown in Table 9, Li2O2 was completely converted into Li2O, when heat-treated at 400° C. or higher for 60 minutes or more.
20 g of NiO and 8.85 g of Li2O were mixed for 5 minutes with a small mixer. Herein, the used Li2O was a sample c of Table 8.
The mixed powder was exposed to 700° C. for 12 hours in a nitrogen atmosphere furnace to synthesize Li2NiO2. The synthesized powder was 28.86 g.
The synthesized Li2NiO2 was used to manufacture a CR2032 coin cell, and electrochemical characteristics thereof were evaluated. An electrode was manufactured by coating an active material layer to be 50 to 80 μm thick on a 14 mm-thick aluminum thin plate.
Electrode slurry was prepared by mixing Li2NiO2: denka black (D.B.): PvdF=85:10:5 wt % and then, coated, vacuum-dried, and pressed to form a coating layer having a final thickness of 40 to 60 μm. An electrolyte solution was an organic solution prepared by using a mixed solvent of EC:EMC=1:2 and dissolving LiPF6 salt at a concentration of 1 M.
The manufactured coin cell was charged and discharged at a 0.1 C-rate, in a CCCV mode under a 1% condition within a range of 4.25 V to 3.0 V. Charge and discharge curves of three coin cells are shown in
The particles according to the examples were clearly distinguished as secondary particles.
Tables 11, 12, and 13 are evaluation data of LNO's resultants obtained by firing two Li2O particles of
LNO's according to the examples exhibited improved characteristics in all aspects.
Table 14 shows the evaluation results of coin cells using LNO's obtained after the firing two Li2O's of
The cell data of the examples were significantly improved.
The present invention may be embodied in many different forms, and should not be construed as being limited to the disclosed embodiments. In addition, it will be understood by those skilled in the art that various changes in form and details may be made thereto without departing from the technical spirit and essential features of the present invention. Therefore, the aforementioned embodiments should be understood to be exemplary but not limiting the present invention in any way.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2018-0134866 | Nov 2018 | KR | national |
This application is the divisional patent application of U.S. patent application Ser. No. 17/291,774, filed on May 6, 2021, which is the U.S. National Phase under 35 U.S.C. § 371 of International Patent Application No. PCT/KR2019/013381, filed on Oct. 11, 2019, which in turn claims the benefit of Korean Patent Application No. 10-2018-0134866, filed on Nov. 6, 2018, the entire disclosures of which applications are incorporated by reference herein.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 17291774 | May 2021 | US |
| Child | 18977261 | US |
