CN105070902A - Mixed transition metal based preparation method for cathode material of sodium secondary battery - Google Patents
Mixed transition metal based preparation method for cathode material of sodium secondary battery Download PDFInfo
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- CN105070902A CN105070902A CN201510418880.9A CN201510418880A CN105070902A CN 105070902 A CN105070902 A CN 105070902A CN 201510418880 A CN201510418880 A CN 201510418880A CN 105070902 A CN105070902 A CN 105070902A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses an organic coprecipitation preparation method for a cathode material NaxMyO2 (M is combination of two or more of Mn, Fe, Co and Ni) of a sodium secondary battery. The preparation method is characterized by comprising the following steps: mixing a solution A, in which a Na source and mixed transition metal raw materials such as a Fe source, a Ni source, a Co source, a Mn source and the like are dissolved, with an organic precipitant solution B in a dropwise-adding manner to generate precipitates; then without filtering, precipitating and washing, directly removing a solvent by steaming to obtain precipitates; and processing the precipitates at a high temperature to obtain a target product. According to the method, in a precipitate forming process, metal ions can be well bonded with an organic precipitant through coordination bonds, very high ion selectivity is achieved, and the generated precipitates are pure, small in particle size and uniform in dispersion. The organic precipitant can be removed by decomposition in a sintering process, so that the preparation process is simplified, the generation of impurities is reduced, and the stoichiometric ratio of the product also can be well controlled. The prepared material is high in purity and uniform in morphology, and has excellent electrochemical performance.
Description
Technical field
The present invention relates to a kind of sodium rechargeable battery Na based on hybrid transition metal
xm
yo
2the preparation method of (two or more combination in M=Mn, Fe, Co, Ni) positive electrode, especially relates to and utilizes Cobalt legal system for high purity N a
xm
yo
2the method of (two or more combination in M=Mn, Fe, Co, Ni) positive electrode, belongs to sodium rechargeable battery field of material technology.
Background technology
At present, the main source of China's energy remains the traditional energies such as coal, oil, fossil fuel, but the economy of energy based on traditional energy also also exists serious problem as harm such as: resource scarcity, non-renewable, environmental pollutions.So we need to go to develop more new forms of energy, such as: wind energy, solar energy, biomass energy, geothermal energy etc.But the factors such as time, space and weather limit large-scale developing and utilizing of regenerative resource, these novel energies all also exist the problems such as efficiency distribution inequality and storage.Therefore novel regenerative resource must by more efficient Conversion of Energy and storage device.In all electro-chemical systems, in secondary cell, lithium ion battery can carry out efficient Conversion of Energy and storage, can provide stable supply of electric power, meets the high request of electrical network and power consumption equipment etc., realizes the Sustainable Development and Utilization of regenerative resource.But considerably less at the content of occurring in nature elemental lithium, only account for 0.006% of earth constituent content, and sodium element can reach 2.74%.Sodium and the same main group of lithium, they have a lot of similarity.The conductor NaAl of high-temperature sodium compound has been it is found that before about 50 years
11o
17, in mid-term in 20th century, people just start to explore the sodium-ion battery manufacturing and be similar to lithium ion battery.
It is found that sodium-ion battery has: the advantages such as energy density is low unlike lithium ion battery, aboundresources, cost are low, economic benefits are good.And, at present along with the development of Novel electronic product, electric automobile, new-generation energy-accumulating power station and intelligent grid etc., to their energy storage device-battery have higher requirement as: high-energy-density, high power density, have extended cycle life, good security performance etc.These require the new standard that also will become the development of following battery.Therefore, sodium-ion battery will occupy a tiny space in following energy storage device system.
Layered oxide is Na such as
xcoO
2, Na
xniO
2, Na
xmnO
2, Na
xtiS
2etc. having reversible embedding de-Na
+ability.But their capacity and high rate performance are all limited, in order to address this problem, the oxide of hybrid transition metal causes pay close attention to widely because it has multiple state of appraising at the current rate.Na
xm
yo
2(two or more combination in M=Ti, V, Cr, Mn, Fe, Co, Ni) is also one of them, is expected to become a kind of power sodium rechargeable battery positive electrode having prospect.
Na
xm
yo
2structure and the preparation method of (in M=Mn, Fe, Co, Ni two or more combination) are closely related, to synthesis temperature and atmosphere very responsive.Solid phase method is the classical preparation method of nearly all positive electrode, but it is high to there is energy consumption, and batch wise differences is large, the shortcomings such as domain size distribution is wide.To Na
xm
yo
2(two or more combination in M=Mn, Fe, Co, Ni), on the one hand, easily forms oxygen disappearance in sintering process, and causes NiO and Na
x ni
1-
x the existence of the dephasigns such as O.On the other hand, concerning the embedding oxidate for lithium of this type of hybrid transition metal based on solid solution, how accurately controlling the stoichiometric proportion of product, is also the problem needing to solve in material preparation process.Therefore, suitable preparation method is most important to electrode material.Not only can obtain by selecting suitable preparation method that particle size shape is suitable for, the controllable appearance of even particle size distribution, more can obtain better crystallinity, higher phase purity and structural stability, thus realize more excellent chemical property.
The synthetic method of a series of nano material, is just progressively incorporated in the preparation of electrode material studied person.The research of current sodium-ion battery positive material is in the development phase, the M.Sathiya of France, and the people such as K.Hemalatha, K.Ramesha adopt sol-gal process to synthesize NaNi
1/3co
1/3mn
1/3o
2, material particle size, at about 1 to 10 μm, presents good cycle performance (M.Sathiya, K.Hemalatha, K.Ramesha, J.-M.Tarascon, A.S.Prakash, Chem.Mater.24 (2012) 1846.).Coprecipitation is approved because it can control the element proportioning in precursor preferably, but the coprecipitation of research is at present all using inorganic base as precipitation reagent, and is avoid precipitation reagent to remain the destruction of OH to material property, needs repeatedly to wash precipitation.No matter and the solution loss in washing process, in washing process, to change the loss of elements brought unbalanced for pH value, still can bring difficulty to the Composition Control of material.In addition, even if pass into inert gas in precipitation process in system, be also difficult to avoid a small amount of ion to be oxidized to high-valence state, this, also for calculating that Na source addition brings uncertainty according to precursor gravimetric method, causes product stoichiometry ratio to be difficult to control.For this reason, the present invention introduces organic precipitant in a creative way, can solve the problem well, and can simplify preparation technology.Utilize organic precipitant coprecipitation, the positive electrode that can be based on solid solution synthesizes, and brings following advantage: (1) organic precipitant is combined with coordinate bond with metal ion, has good ion selectivity, and the precipitation of generation is pure and solubility is very little; (2) select suitable precipitation reagent, precipitation nucleation can be made to separate with growth course, thus control nucleus is synchronously grown up, and obtains the molecule of size uniform; (3) organic precipitant can decompose removing in sintering process, therefore can washing precipitation precursor, thus both simplifies preparation technology, can control again the stoichiometric proportion of product well.
Summary of the invention
The object of the invention is to for a kind of sodium rechargeable battery Na based on hybrid transition metal
xm
yo
2(M=Mn, Fe, Co, two or more combination in Ni) be difficult to the stoichiometric proportion accurately controlling product in preparation process, easily form dephasign and cause the problems such as chemical property variation, providing a kind of technological operation simple, product purity is high, and pattern evenly prepares Na
xm
yo
2the Cobalt preparation method of (two or more combination in M=Mn, Fe, Co, Ni) positive electrode.
Preparation method of the present invention comprises the following steps:
1) the hybrid transition metal raw materials such as the soluble sodium source of certain stoichiometric proportion, source of iron, nickel source, cobalt source and manganese source are added to the water respectively, after being uniformly mixed, obtain mixed solution A;
2) weigh organic precipitant according to the certain proportion with metal ion, be dissolved under uniform temperature in organic solvent and obtain solution B;
3) under maintaining uniform temperature and Keep agitation, by the mixed solution A of step 1) gained and step 2) solution B of gained mixes in the mode dropwise dripped, is added dropwise to complete rear continuation and stirs a period of time, constantly generate precipitation in this process;
4) by the precipitated dispersion system of step 3) gained, without the need to filtering and washing of precipitate, direct evaporation drying is removed desolventizing and is precipitated thing;
5) under certain atmosphere, rise to high temperature sintering a period of time with certain heating rate by after the sediment of step 4) gained under a certain pressure base, after being then cooled to room temperature with certain rate of temperature fall, grind and obtain target product Na
xm
yo
2(two or more combination in M=Mn, Fe, Co, Ni).
The mol ratio of the hybrid transition metal total amounts such as described sodium source and source of iron, nickel source, cobalt source and manganese source is 1:1, and wherein sodium source can be suitably excessive.
Described sodium source compound is at least one in sodium acetate, sodium chloride, NaOH, sodium nitrate.
Described hybrid transition metal raw material is at least one in acetate, sulfate, nitrate, chlorate, the fluoride salts such as iron, nickel, cobalt, manganese.
The ratio of described organic precipitant and metal ion "
n(precipitation reagent):
n(total metal ion) " be (1 ~ 3): 1.
Described organic precipitant is at least one in oxine, sodium tetraphenylborate, crystal violet etc.
Described organic solvent is at least one in methyl alcohol, ethanol, isopropyl alcohol, cyclohexane, acetonitrile, 1-METHYLPYRROLIDONE etc.
The described hybrid mode dropwise dripped is for be dropwise added drop-wise to solution A in solution B, or solution B is dropwise added drop-wise in solution A, or solution A and solution B is dropwise added drop-wise in another container simultaneously.
Described precipitated dispersion system evaporation drying except the mode of desolventizing be heating water bath evaporation, drying box dries, at least one in vacuumize, baking temperature is 60 ~ 120 DEG C.
The pressure of described precursor powder compressing tablet base is 1 ~ 10MPa.
Described sintering atmosphere is at least one in air, oxygen, nitrogen, argon gas, helium.
Described calcining heat is 800 ~ 900 DEG C, and calcination time is 6 ~ 14h, and calcination process heating rate is intensification per minute 1 ~ 20 DEG C.
The described type of cooling is program control slow cooling, in stove, cooling, post-calcination sample directly take out fast cooling, sample is dropped into quenching-in water naturally, sample is dropped at least one in quenching in liquid nitrogen.
Accompanying drawing explanation
In order to be illustrated more clearly in technical scheme of the present invention, in describing the present invention and embodiment below, the required accompanying drawing used does simple introduction.Apparently, the accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, can also obtain other accompanying drawings according to these accompanying drawings.
Fig. 1 is Na prepared by the present invention
xm
yo
2the x-ray diffraction pattern of (two or more combination in M=Mn, Fe, Co, Ni) positive electrode sample.As seen from Figure 1, material crystalline is fine, has good layer structure.
Fig. 2 is Na prepared by the present invention
xm
yo
2(two or more combination in M=Mn, Fe, Co, Ni) positive electrode sample discharge curve under different multiplying electric current.As seen from Figure 3, prepared Na
xm
yo
2(in M=Mn, Fe, Co, Ni two or more combination) material still has good high rate performance when not extra carbon dope.
Fig. 3 is Na prepared by the present invention
xm
yo
2the circulation curve chart of (two or more combination in M=Mn, Fe, Co, Ni) positive electrode sample.As seen from Figure 3, prepared Na
xm
yo
2(in M=Mn, Fe, Co, Ni two or more combination) material has good high rate performance and reaction invertibity, does not only decay getting back to little rate capability after different large multiplying power dischargings, promotes to some extent on the contrary.
Embodiment
For the ease of understanding the present invention, below in conjunction with specific embodiment, the present invention is described in further detail.Obviously, described embodiment is only section Example of the present invention, instead of whole embodiments.Based on embodiments of the invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to protection scope of the present invention.
Embodiment 1
0.03mol sodium acetate, 0.01mol nickel acetate, 0.01mol cobalt acetate, 0.01mol manganese acetate are added in deionized water respectively, after being uniformly mixed, obtains mixed solution A; Take 0.06mol organic precipitant oxine, be dissolved at 60 DEG C in ethanol, obtain solution B.Under maintenance 60 DEG C and continuing magnetic force are stirred, slowly solution A is dropwise added drop-wise in solution B, is added dropwise to complete rear continuation and stirs 2h, in this process, constantly generate precipitation.This precipitated dispersion is tied up to 80 DEG C of water-bath evaporation of solvent, then in 100 DEG C of vacuum drying chambers dry 10h, be precipitated thing.At 10MPa tableting under pressure base after sediment is ground, rise to 850 DEG C of insulation 12h with the heating rate of 10 DEG C/min in air atmosphere, after being then cooled to room temperature with the rate of temperature fall of 1 DEG C/min, grind and obtain target product NaNi
1/3co
1/3mn
1/3o
2.The X-ray powder diffraction figure of sample, see Fig. 1, shows prepared NaNi
1/3co
1/3mn
1/3o
2material phase purity is high, good crystallinity.The scanning electron microscope (SEM) photograph of sample is see Fig. 2, and the even particle size of product as seen from the figure, particle diameter is about 150nm.Using the product of gained as positive electrode, excessive sodium is as negative pole, experiment button sodium rechargeable battery is assembled in the glove box being full of argon gas, in the potential region of 1.5 ~ 4.0V, charge and discharge cycles is carried out with the electric current of 14mA/g, specific discharge capacity can reach 106mAh/g, specific discharge capacity under the electric current of 1440mA/g can reach 70mAh/g, reversible capacity after circulating through different multiplying 45 weeks can remain on 110mAh/g, capacity is not only decayed and is promoted to some extent on the contrary, demonstrates excellent chemical property.
Embodiment 2
0.03mol sodium oxalate, 0.02mol cobalt oxalate, 0.02mol nickel oxalate, 0.03mol ferric oxalate are added in deionized water respectively, dissolve, be uniformly mixed after obtain mixed solution A; Take 0.06mol organic precipitant dinitroaniline, be dissolved at 50 DEG C in cyclohexane, obtain solution B.Under continuing magnetic force stirs, slowly solution B is dropwise added drop-wise in solution A, is added dropwise to complete rear continuation and stirs 3h, in this process, constantly generate precipitation.This precipitated dispersion is tied up to 85 DEG C of water-bath evaporation of solvent, then in 110 DEG C of dried in vacuo overnight, be precipitated thing.At 8MPa tableting under pressure base after sediment is ground, under oxygen atmosphere, rise to 800 DEG C of insulation 14h with the heating rate of 5 DEG C/min, after being then cooled to room temperature with the rate of temperature fall of 0.5 DEG C/min, grind and obtain target product NaCo
2/3ni
2/3feO
2.
Embodiment 3
0.01mol NaOH, 0.02mol cobalt chloride, 0.01mol manganese chloride are added in deionized water respectively, dissolve, be uniformly mixed after obtain mixed solution A; Take 0.06mol organic precipitant dimethylglyoxime, be dissolved at 70 DEG C in isopropyl alcohol, obtain solution B.Under continuing magnetic force stirs, slowly solution A and solution B are dropwise added drop-wise in beaker simultaneously, in this process, constantly generate precipitation, be added dropwise to complete rear continuation and stir 5h.This precipitated dispersion is tied up to 100 DEG C of water-bath evaporation of solvent, then in 120 DEG C of air dry ovens dry 12h, be precipitated thing.At 12MPa tableting under pressure base after sediment is ground, rise to 850 DEG C of insulation 6h with the heating rate of 15 DEG C/min in a nitrogen atmosphere, after then cooling to room temperature with the furnace, grind and obtain target product Na
1/3co
2/3mn
1/3o
2.
Embodiment 4
0.03mol sodium carbonate, 0.03mol chromic nitrate, 0.03mol manganese nitrate are added in deionized water respectively, dissolve, be uniformly mixed after obtain mixed solution A; Take 0.06mol organic precipitant dinitroaniline, be dissolved at 65 DEG C in 1-METHYLPYRROLIDONE, obtain solution B.Under continuing magnetic force stirs, slowly solution A is dropwise added drop-wise in solution B, in this process, constantly generates precipitation, be added dropwise to complete rear continuation and stir 6h.This precipitated dispersion is tied up to 85 DEG C of water-bath evaporation of solvent, then in 115 DEG C of vacuumize 16h, be precipitated thing.At 6MPa tableting under pressure base after sediment is ground, 900 DEG C of insulation 12h are risen in air atmosphere with the heating rate of 8 DEG C/min, then sample is directly taken out to drop in deionized water at room temperature and quenches, then in 120 DEG C of air dry ovens dried overnight, namely obtain target product NaCrMnO after grinding
2.
Claims (9)
1. the sodium rechargeable battery positive electrode Na based on hybrid transition metal
xm
yo
2(M=Mn, Fe, Co, in Ni two or more combination) Cobalt preparation method, it is characterized in that adopting Cobalt legal system for this material first, organic precipitant can decompose removing in sintering process, thus both simplifies preparation technology, decrease the generation of impurity, the stoichiometric proportion of product can be controlled again well.
2. Na as claimed in claim 1
xm
yo
2the Cobalt preparation method of (two or more combination in M=Mn, Fe, Co, Ni) positive electrode, its feature mainly comprises the following steps:
1) the hybrid transition metal raw materials such as the soluble sodium source of certain stoichiometric proportion, source of iron, nickel source, cobalt source and manganese source are added to the water respectively, after being uniformly mixed, obtain mixed solution A;
2) weigh organic precipitant according to the certain proportion with metal ion, under uniform temperature, be uniformly mixed to obtain solution B;
3) under maintenance uniform temperature and Keep agitation, by the mixed solution A of step 1) gained and step 2) solution B of gained mixes in the mode dropwise dripped, is added dropwise to complete rear continuation stirring a period of time, constantly generates precipitation in this process;
4) by the precipitated dispersion system of step 3) gained, without the need to filtering and washing of precipitate, directly evaporation drying is removed desolventizing and is precipitated thing at a certain temperature;
5) by after the sediment of step 4) gained under a certain pressure base under certain atmosphere, through uniform temperature calcining, after being then cooled to room temperature with certain rate of temperature fall, grind and obtain target product Na
xm
yo
2(two or more combination in M=Mn, Fe, Co, Ni).
3. Na as claimed in claim 2
xm
yo
2the Cobalt preparation method of (two or more combination in M=Mn, Fe, Co, Ni) positive electrode, is characterized in that the mol ratio of the hybrid transition metal total amount such as described sodium source and source of iron, nickel source, cobalt source and manganese source is 1:1; Described sodium source compound is at least one in sodium acetate, sodium chloride, NaOH, sodium nitrate, and described hybrid transition metal raw material is at least one in the acetate of iron, nickel, cobalt, manganese etc., sulfate, nitrate, chlorate, fluoride salt.
4. Na as claimed in claim 2
xm
yo
2the Cobalt preparation method of (in M=Mn, Fe, Co, Ni two or more combination) positive electrode, it is characterized in that described organic precipitant and metal ion ratio "
n(precipitation reagent):
n(total metal ion) " be (1 ~ 3): 1; Described organic precipitant is at least one in oxine, methylene blue, dinitroaniline etc.; Described organic solvent is at least one in methyl alcohol, ethanol, isopropyl alcohol, acetonitrile etc.; .
5. Na as claimed in claim 2
xm
yo
2(M=Mn, Fe, Co, two or more combination in Ni) the Cobalt preparation method of positive electrode, the hybrid mode dropwise dripped described in it is characterized in that is for be dropwise added drop-wise to solution A in solution B, or solution B is dropwise added drop-wise in solution A, or solution A and solution B are dropwise added drop-wise in another container simultaneously.
6. Na as claimed in claim 2
xm
yo
2the Cobalt preparation method of (two or more combination in M=Mn, Fe, Co, Ni) positive electrode, being added dropwise to complete rear continuation mixing time described in it is characterized in that is 2 ~ 6h; The temperature of described maintenance is 60 ~ 70 DEG C.
7. Na as claimed in claim 2
xm
yo
2(M=Mn, Fe, Co, two or more combination in Ni) the Cobalt preparation method of positive electrode, it is characterized in that described precipitated dispersion system evaporation drying except the mode of desolventizing be heating water bath evaporation, drying box dries, at least one in vacuumize, baking temperature is 60 ~ 120 DEG C; The pressure of described sediment compressing tablet base is 1 ~ 10MPa.
8. Na as claimed in claim 2
xm
yo
2the Cobalt preparation method of (two or more combination in M=Mn, Fe, Co, Ni) positive electrode, is characterized in that described sintering atmosphere is at least one in air, oxygen, nitrogen, argon gas, helium.
9. Na as claimed in claim 1
xm
yo
2the Cobalt preparation method of (two or more combination in M=Mn, Fe, Co, Ni) positive electrode, it is characterized in that described calcining heat is 800 ~ 950 DEG C, calcination time is 6 ~ 14h, and calcination process heating rate is intensification per minute 1 ~ 20 DEG C; The described type of cooling is program control slow cooling, in stove, cooling, post-calcination sample directly take out fast cooling, sample is dropped into quenching-in water naturally, sample is dropped at least one in quenching in liquid nitrogen.
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| CN107403915A (en) * | 2017-07-13 | 2017-11-28 | 南京大学 | The manganese-based anode material of sodium-ion battery |
| CN107946588A (en) * | 2017-11-15 | 2018-04-20 | 上海空间电源研究所 | A kind of O3 types sodium-ion battery positive material, preparation method and the usage |
| CN108110236A (en) * | 2017-12-14 | 2018-06-01 | 东北大学 | A kind of sodium-ion battery positive material and preparation method thereof |
| CN108232177A (en) * | 2018-02-22 | 2018-06-29 | 济南大学 | It is a kind of for composite positive pole of sodium-ion battery and preparation method thereof |
| CN108232177B (en) * | 2018-02-22 | 2020-06-19 | 济南大学 | Composite positive electrode material for sodium ion battery and preparation method thereof |
| CN109659520A (en) * | 2018-12-07 | 2019-04-19 | 北京化工大学 | A kind of preparation of sodium ion energy storage device positive and negative electrode material and its symmetrical energy storage device |
| CN109659520B (en) * | 2018-12-07 | 2022-05-10 | 北京化工大学 | Application of battery material in positive electrode and negative electrode of sodium ion battery |
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Application publication date: 20151118 |