CN102408120B - Method for preparing high-purity ultrafine lithium-carbonate micro powder - Google Patents
Method for preparing high-purity ultrafine lithium-carbonate micro powder Download PDFInfo
- Publication number
- CN102408120B CN102408120B CN201010287696.2A CN201010287696A CN102408120B CN 102408120 B CN102408120 B CN 102408120B CN 201010287696 A CN201010287696 A CN 201010287696A CN 102408120 B CN102408120 B CN 102408120B
- Authority
- CN
- China
- Prior art keywords
- lithium
- carbonate
- micro powder
- quilonum retard
- ultrafine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention relates to a method for preparing high-purity ultrafine lithium-carbonate micro powder, which is characterized in that primary lithium carbonate (purity: less than 95%) and CO2 gas are taken as raw materials, and through adopting a new efficient carbonization device, the insoluble lithium carbonate is converted into large-solubility lithium bicarbonate; and after a lithium bicarbonate solution is purified, in a spray drying device, the decomposition of the lithium bicarbonate solution and the crystallization and drying of the lithium carbonate are completed in one step, and then an ultrafine lithium-carbonate micro powder product is directly obtained. The method disclosed by the invention has the advantages that the method is simple in process, excellent in product, stable in quality, high in recovery rate and convenient for industrialization; the prepared ultrafine lithium-carbonate micro powder has a porous hollow sphere structure (D0.5 can be less than 5 microns) formed by carrying out self-assembling on lithium-carbonate crystalline granules (about 200 nm); the BET specific surface area of the ultrafine lithium-carbonate micro powder can reach 7 m<2>/g, which is far higher than that of a product prepared by using the existing method, therefore, the method has a strong application value in the industries such as lithium ion batteries and the like.
Description
[technical field]
The present invention relates to the Quilonum Retard technical field, specifically, is a kind of method for preparing high-purity ultrafine lithium-carbonate micro powder.
[background technology]
As basic lithium salts, Quilonum Retard all has a wide range of applications in industries such as glass, pottery, aluminium metallurgy, information, nuclear industry, medicine.It is also the main raw material of manufacturing metallic lithium and isotropic substance thereof, various meticulous lithium salts (lithium molybdate, lithium hydroxide, lithiumbromide etc.).Highly purified Quilonum Retard (being greater than 99.9%) is the requisite of lithium ion battery, magneticsubstance, electronic material and opticinstrument, after entering 21 century, along with the high speed development of New Energy Industry and information industry, growing to the demand of pure Lithium Carbonate both at home and abroad.Therefore, highly purified Quilonum Retard just more and more receives publicity, and powerful growth momentum is arranged.
Some high-tech applications are except Quilonum Retard purity is had to strict requirement, to the granularity of Quilonum Retard particle and pattern also very high requirement.Such as, in recent years, along with day by day highlighting of energy problem, the development of lithium ion battery, especially power-type lithium ion battery is in the ascendant.Quilonum Retard is the main raw material of anode material for lithium-ion batteries (lithium manganate, cobalt acid lithium, iron lithium phosphate etc.); Quilonum Retard joins in battery as the additive of electrolytic solution, can improve the film forming properties of battery, thereby improves cycle performance and the low temperature performance of battery.Battery carbon acid lithium at least will meet the requirement of two aspects: at first Quilonum Retard will have very high purity, and secondly the granularity of Quilonum Retard is as much as possible little.
The preparation method of pure Lithium Carbonate mainly comprises Zint1-Harder-Dauth method, recrystallization method, the causticization precipitator method, carbonization decomposition method etc.Wherein, the carbonization decomposition method is expected most, and this method raw material is relatively inexpensive to be easy to get, and technique is simple, process environmental protection, the Li made
2cO
3particle diameter is large, and the rate of recovery is high, has higher operation possibility.It mainly comprises carbonization process and thermal decomposition process, and its principle can be expressed as:
Li
2CO
3+CO
2+H
2O→2LiHCO
3
2LiHCO
3→Li
2CO
3↓+CO
2↑+H
2O
Its technical process is as follows.Elementary Li
2cO
3(purity is less than 95%) is mixed into aqueous solution slip with deionized water, in the situation that stir, leads to wherein the high-purity CO of people
2gas.Control suitable temperature of reaction, stirring velocity and CO
2the speed that passes into, control the suitable reaction times, change the Quilonum Retard of indissoluble into lithium bicarbonate that solubleness is larger.Then filter slip to remove insoluble impurity.The impurity be dissolved in filtrate can be removed by methods such as ion-exchange and extractions.Lithia water add thermal purification in another reactor after, constant temperature stirs removes CO
2gas, lithium bicarbonate will decompose precipitation and generate Li
2cO
3.Through cooling, filter out precipitation again, then at suitable temperature, dry and obtain highly purified Li
2cO
3product.
Current, all there are certain defect in the carbonization technique of carbonization decomposition method and thermal decomposition process, need further improve.For carbonization process, at present main application machine steel basin carries out carbonization, in order to enhance productivity, just increases working pressure.Adopt higher pressure exerting device to carry out carbonization, increased facility investment and process cost, be not easy to production control and continuous operation.According to the gas liquid reaction theory, partial pressure and liquid-gas interface are the important factors that affects body series gas liquid reaction speed, thereby can increase liquid-gas interface by the form of improving gas-liquid reactor (carbonizer), to reach the higher carbonization efficiency of acquisition under the moderate pressure condition.For thermal decomposition process, pyrolysis carries out in the heated and stirred still, Li
2cO
3particle is assembled seriously each other, and granularity is larger, is not easy to direct application, must be through pulverizing the demand to lithium carbonate product such as the industry that could meet lithium ion battery.In the pyrolysis process, Li
2cO
3the crystal wall sticking phenomenon is very serious, and the generation of brilliant dirt has reduced heat transfer efficiency and production efficiency, has increased energy consumption and cleaning maintenance cost.
Obtain the method for fine granularity Quilonum Retard in prior art, mainly comprise mechanical crushing method, solid phase method, mixed phase method, liquid phase method (precipitator method) and vapor phase process.But prior art still mainly relies on disintegrating apparatus to realize to the control of Quilonum Retard the finished product granularity.
CN 1267636A discloses a kind of preparation method of sulfuric acid process to produce battery-level lithium carbonate.Its production technique is that made the transition roasting, acidizing fired, leaching, purifying treatment, concentration, sinker processing, cleaning, drying treatment, pulverizing, package processing of lithium concentrate formed.The method be take lithium concentrate as raw material, but may not be suitable for the lithium resource existed with the salt lake brine form.Although the purity of the Quilonum Retard obtained by the method can meet the requirement of battery, obviously the method is very loaded down with trivial details, production technique is too complicated, and, due to the restriction of disintegrating apparatus grindability, the granularity of the Quilonum Retard primary particle obtained is micron order.
CN 101209846A discloses a kind of preparation method of nano-scale lithium carbonate for battery, and the method is included in the aqueous solution, by lithium hydroxide or water-soluble lithium salts and carbonic acid gas or water soluble carbonate contact reacts.Contact reacts is carried out under dispersion agent exists, and described dispersion agent is with the water soluble anionic surfactant of carboxylic acid ester groups and/or sulfonate group and/or organic amine.The method can access the granularity of thinner Quilonum Retard, but the method is higher to the purity requirement of feed hydrogen Lithium Oxide 98min or water-soluble lithium salts; Operational cycle very long (the gas liquid reaction time in the specific embodiment that CN101209846A provides generally reaches 20-40 hour, and digestion time reaches 24 hours, reaches 48 hours time of drying); In gas-liquid reaction process, Quilonum Retard is easily assembled the obstruction vent line; And the gained lithium carbonate product still needs through subsequent disposal such as filtering, wash, be dry.
So research purpose of the present invention, for take carbonization decomposition method principle as basis, is sought a kind of simple processing method efficiently, prepares high-purity ultrafine lithium-carbonate micro powder, to meet the demand of the industry such as lithium ion battery to high-end lithium carbonate product.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, a kind of method for preparing high-purity ultrafine lithium-carbonate micro powder is provided.
The objective of the invention is to be achieved through the following technical solutions:
A kind of method for preparing high-purity ultrafine lithium-carbonate micro powder, is characterized in that, concrete steps are: with first level lithium carbonate and CO
2gas is raw material, adopts new and effective carbonizing apparatus, replaces traditional mechanical agitating tank to carry out carbonization, changes the Quilonum Retard of indissoluble into lithium bicarbonate that solubleness is larger; Remove insoluble impurities by filtering slip, remove the foreign ion be dissolved in filtrate by ion-exchange; The decomposition drying process of the lithia water after purification, in spray drying device, a step completes, and directly obtains Quilonum Retard ultra-fine micropowder product; Do not need further processing treatment.Rather than, as traditional technology, thermal degradation lithia water in stirring tank, obtain passing through the subsequent operationss such as filtration, washing, drying, pulverizing after the Quilonum Retard precipitation again.
The preparation method of high-purity ultrafine lithium-carbonate micro powder provided by the invention be take first level lithium carbonate as raw material; If just the level lithium carbonate crystal size is larger, in order to obtain higher carbonization efficiency, the Quilonum Retard raw material can be carried out to pulverization process, breaking method can be ball mill pulverizing, comminution by gas stream and ultrasonication etc.
In carbonizing apparatus, elementary lithium carbonate aqueous solution slip and CO
2gas carries out carburizing reagent and generates lithium bicarbonate; CO
2gas and Li
2cO
3carburizing reagent in the aqueous solution is the gas-liquid-solid phase reaction process that a mass transfer process and chemical reaction process carry out simultaneously, and the essence of reaction is still the ionic reaction in the aqueous solution, and crucial step is exactly CO
2the dissolving of gas and Li
2cO
3mass transfer process; The factor that affects carburizing reagent is a lot, as Li
2cO
3the temperature of the massfraction of slurries (solid-to-liquid ratio of reaction), reaction, the speed, the CO that have or not stirring and stir
2dividing potential drop, reaction times etc.
The present invention selects new and effective carbonizing apparatus to strengthen carburizing reagent, improves carburizing reagent speed and CO
2utilization ratio; Comprise falling-film tower (wet-wall tower), spray tower, bubble tower and rotating disk (rotation film) reactor; Working pressure is 0～1.0Mpa, and service temperature is 5～65 ℃; [Li during the carbonization terminal
+] concentration should be more than 0.5mol/L.Because the liquid-gas interface of the new and effective carbonizing apparatus such as falling-film tower (wet-wall tower) is more much higher than mechanical agitating tank, so, under the same operation condition, its carbonization efficiency far is higher than mechanical agitating tank.
Slip after carbonization is filtered, removed insoluble impurities, as molysite, silico-aluminate etc.; By filtrate successively by anion and cation exchange resin with foreign ions such as the calcium of removing solubility wherein, magnesium.
Lithia water after purifying is transported in spray drying device, sprays and decompose drying, service temperature is 60～600 ℃; Spray drying device of the present invention does not have special requirement to spray pattern, and no matter the forms such as air-flowing type, centrifugal or ultrasonic type, as long as spray droplet is enough little, all can obtain satisfactory product.
The prepared Quilonum Retard micro mist of the present invention has porous hollow spherical structure (d
50can be as small as below 5 microns), its secondary structure is about 200 nano lithium carbonate crystal grains; The BET specific surface area of this Quilonum Retard micro mist can reach 7m
2more than/g, higher than the specific surface area that has the prepared product of method, (the highest BET specific surface area of having reported is 2.79m far away
2/ g), there is very strong using value.
Compared with prior art, positively effect of the present invention is:
Method provided by the present invention, technique is simple, product fine, steady quality, the rate of recovery is high, is convenient to industrialization.
[accompanying drawing explanation]
Fig. 1 normal pressure descending film absorbs the carbonization Experimental equipment;
Fig. 2 ion exchange unit figure;
Fig. 3 sprays and decomposes drying installation figure;
Fig. 4 sprays and decomposes drying products XRD spectra and the comparison of standard spectrogram;
Fig. 5 a, the drying products pattern is decomposed in the 5b spraying;
Fig. 6 sprays and decomposes the drying products size-grade distribution;
Mark in accompanying drawing is respectively: 1, CO
2steel cylinder, 2, film-falling absorption tower, 3, recycle pump, 4, mechanical stirring, 5, steel basin, 6, thermostatic bath, 7, anion-exchange column, 8, cationic exchange coloum, 9, transferpump, 10, heating chamber, 11, the product-collecting bottle.
[embodiment]
The present invention below is provided a kind of embodiment for preparing the method for high-purity ultrafine lithium-carbonate micro powder.
The present embodiment mainly comprises that Quilonum Retard carbonization, lithia water purify and dry three steps are decomposed in the lithia water spraying:
(1) Quilonum Retard carburising step: the present embodiment operation adopts falling-film tower (wet-wall tower) to carry out carbonization, and Fig. 1 is shown in by concrete experimental installation.Operation steps is as follows: add 300～500ml deionized water in tower reactor, open mechanical stirring, recycle pump and water bath with thermostatic control.Stirring velocity is 0～1000rpm, and the liquid circulation flow is: 0.1～10L/min.When the deionized water homo(io)thermism is 5～55 ℃, add 10～50gLi
2cO
3powder, open CO
2steel cylinder, start timing.By pressure maintaining valve and gas meter adjustments of gas apparent velocity, at 0.2～2L/min, falling-film tower (wet-wall tower) working pressure is normal pressure.When reaching requirement, lithium concentration stops carburizing reagent;
(2) lithium bicarbonate purifying step: the slip after carbonization is filtered, remove insoluble impurities.By filtrate successively by the yin, yang ion exchange column to remove the wherein foreign ion (see figure 2) of solubility;
(3) drying step is decomposed in spraying: the lithia water after purifying is transported in spray drying device, sprays and decompose drying, service temperature is 60-560 ℃.Directly obtain Quilonum Retard ultra-fine micropowder product (see figure 3).
Product characterizes:
The product of the high-purity ultrafine lithium-carbonate micro powder that adopts X-ray diffraction analysis (XRD) to prepare the present embodiment has carried out structural characterization.Its XRD figure spectrum (see figure 4) and Quilonum Retard standard x RD collection of illustrative plates are identical.
The product of the high-purity ultrafine lithium-carbonate micro powder that adopts scanning electron microscope (SEM) to prepare the present embodiment has carried out morphology characterization (seeing Fig. 5 a, 5b).The demonstration of SEM image, the Quilonum Retard micro mist has the porous hollow spherical structure, the Quilonum Retard crystal grain that its secondary structure is approximately 200 nanometers.
Adopt Ma Erwen particle-size analyzer (Mastersizer 2000, Malvren, UK) to carry out granularity to the product of originally executing the routine high-purity ultrafine lithium-carbonate micro powder prepared and characterize (see figure 6), d
50it is 4.00 microns.What it should be noted that the reflection of these particle size distribution figures is only the information of macroscopical hollow ball, and the dimension information of the small crystal of secondary structure must depend on the instruments such as scanning electron microscope, transmission electron microscope and observes.
Adopt BET specific surface area analysis instrument (TriStar 3000, Micromeritics, US) to carry out the specific surface area sign to the product of originally executing the routine high-purity ultrafine lithium-carbonate micro powder prepared.The BET specific surface area is 7.24m
2more than/g, higher than the specific surface area that has the prepared product of method, (the highest BET specific surface area of having reported is 2.79m far away
2/ g).
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (2)
1. a method for preparing high-purity ultrafine lithium-carbonate micro powder, is characterized in that, concrete steps are: with first level lithium carbonate and CO
2gas is raw material, adopts carbonizing apparatus, changes the Quilonum Retard of indissoluble into lithium bicarbonate that solubleness is larger; Remove insoluble impurities by filtering slip, remove the foreign ion be dissolved in filtrate by ion-exchange; The decomposition drying process of the lithia water after purification, in spray drying device, a step completes, and directly obtains Quilonum Retard ultra-fine micropowder product;
In spray drying device, the lithia water after purifying is transported in spray drying device, to spray and decompose drying, service temperature is 60～600 ℃;
Described Quilonum Retard micro mist has the porous hollow spherical structure, and its secondary structure is 200 nano lithium carbonate crystal grains, and its BET specific surface area can reach 7m
2more than/g;
Described carbonizing apparatus is falling-film tower, spray tower, bubble tower or rotating disk reactor; Working pressure is 0～1.0MPa, and service temperature is 5～65 ℃; [Li during the carbonization terminal
+] concentration is more than 0.5mol/L.
2. a kind of method for preparing high-purity ultrafine lithium-carbonate micro powder as claimed in claim 1, is characterized in that, first level lithium carbonate raw material is carried out to pulverization process, and breaking method is ball mill pulverizing, comminution by gas stream and ultrasonication.
3. a kind of method for preparing high-purity ultrafine lithium-carbonate micro powder as claimed in claim 1, is characterized in that, in carbonizing apparatus, and elementary lithium carbonate aqueous solution slip and CO
2gas carries out carburizing reagent and generates lithium bicarbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010287696.2A CN102408120B (en) | 2010-09-20 | 2010-09-20 | Method for preparing high-purity ultrafine lithium-carbonate micro powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010287696.2A CN102408120B (en) | 2010-09-20 | 2010-09-20 | Method for preparing high-purity ultrafine lithium-carbonate micro powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102408120A CN102408120A (en) | 2012-04-11 |
| CN102408120B true CN102408120B (en) | 2014-01-01 |
Family
ID=45910521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010287696.2A Active CN102408120B (en) | 2010-09-20 | 2010-09-20 | Method for preparing high-purity ultrafine lithium-carbonate micro powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102408120B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539169A (en) * | 2013-10-24 | 2014-01-29 | 中国地质科学院郑州矿产综合利用研究所 | Method for preparing battery-grade lithium carbonate or high-purity lithium carbonate by using industrial-grade lithium carbonate |
| CN106430260B (en) * | 2016-12-13 | 2017-11-24 | 宜春银锂新能源有限责任公司 | A kind of lepidolite prepares the preparation method of high-purity lithium carbonate |
| CN106517259B (en) * | 2016-12-19 | 2018-07-10 | 天齐锂业股份有限公司 | A kind of spherical Lithii carbonate and preparation method thereof |
| CN108011150A (en) * | 2017-12-28 | 2018-05-08 | 许昌学院 | A kind of method that lithium carbonate is produced from waste and old ternary lithium ion cell electrode powder |
| CN110817908A (en) * | 2018-08-13 | 2020-02-21 | 中国石油化工股份有限公司 | System and method for preparing high-purity lithium carbonate by using lithium-containing waste material |
| CN110563009A (en) * | 2019-09-29 | 2019-12-13 | 华东理工大学 | Method for preparing battery-grade lithium carbonate from fly ash by carbonization decomposition method |
| CN111439761A (en) * | 2020-02-19 | 2020-07-24 | 江西赣锋锂业股份有限公司 | Method for preparing high-purity lithium carbonate through continuous carbonization and decomposition |
| CN111547734A (en) * | 2020-05-11 | 2020-08-18 | 蒋达金 | Preparation method of carbon-doped lithium iron borate |
| CN112479235A (en) * | 2020-12-23 | 2021-03-12 | 江苏容汇通用锂业股份有限公司 | Preparation method of hollow spherical lithium carbonate |
| CN114368765B (en) * | 2021-08-20 | 2023-09-22 | 山东泰普锂业科技有限公司 | Morphology control method of smooth-surface lithium carbonate nanosheets for lithium supplementing of positive electrode in lithium ion battery |
| CN113636577A (en) * | 2021-08-25 | 2021-11-12 | 金川集团股份有限公司 | Preparation method of low-magnetism spherical high-purity lithium carbonate |
| CN115321564B (en) * | 2022-08-31 | 2024-01-30 | 天齐创锂科技(深圳)有限公司 | Long rod-shaped lithium carbonate and preparation method thereof |
| CN115784190A (en) * | 2022-11-30 | 2023-03-14 | 湖北万润新能源科技股份有限公司 | Preparation method of lithium iron phosphate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177288A (en) * | 2007-10-30 | 2008-05-14 | 中国科学院青海盐湖研究所 | Process for preparing high-purity lithium carbonate by using saline lithium resource |
| JP4444121B2 (en) * | 2003-01-08 | 2010-03-31 | 日鉱金属株式会社 | Material for positive electrode of lithium secondary battery and manufacturing method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6048507A (en) * | 1997-12-09 | 2000-04-11 | Limtech | Process for the purification of lithium carbonate |
-
2010
- 2010-09-20 CN CN201010287696.2A patent/CN102408120B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4444121B2 (en) * | 2003-01-08 | 2010-03-31 | 日鉱金属株式会社 | Material for positive electrode of lithium secondary battery and manufacturing method thereof |
| CN101177288A (en) * | 2007-10-30 | 2008-05-14 | 中国科学院青海盐湖研究所 | Process for preparing high-purity lithium carbonate by using saline lithium resource |
Non-Patent Citations (5)
| Title |
|---|
| JP特许第4444121号B2 2010.01.22 |
| Refining of crude Li2CO3 via slurry phase dissolution using CO2;Yi Wen tao et al.;《Separation and Purification Technology》;20071231;第56卷;241-248 * |
| Yi Wen tao et al..Refining of crude Li2CO3 via slurry phase dissolution using CO2.《Separation and Purification Technology》.2007,第56卷241-248. |
| 汪明礼 等.高纯碳酸锂的制备工艺研究.《石油化工应用》.2008,第27卷(第4期),21-26. |
| 高纯碳酸锂的制备工艺研究;汪明礼 等;《石油化工应用》;20080831;第27卷(第4期);21-26 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102408120A (en) | 2012-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102408120B (en) | Method for preparing high-purity ultrafine lithium-carbonate micro powder | |
| CN106335922B (en) | A kind of preparation method of the ultra-thin anatase nanometer sheet self-assembly microspheres in height (001) face | |
| CN103958412A (en) | Process for producing lithium carbonate from concentrated lithium brine | |
| CN113264821B (en) | Recovery method and application of lithium iron phosphate waste | |
| CN102757075B (en) | Method for preparing calcium carbonate powders of different structures and shapes | |
| CN104692465B (en) | The preparation method of anode material for lithium-ion batteries α-LiFeO2 nano-powder | |
| CN110980677B (en) | Method for preparing lithium iron phosphate precursor by using defective ferric phosphate | |
| CN102408119A (en) | Method for preparing lithium carbonate superfine powder through solvating-out and reaction crystallization | |
| Liu et al. | Preparation of lithium carbonate by thermal decomposition in a rotating packed bed reactor | |
| CN110040782A (en) | A kind of manganese dioxide, and its preparation method and application | |
| CN103553067B (en) | The method of full potassium W type molecular sieve produced by a kind of KOH alkali fusion activation potassium felspar sand | |
| Wang et al. | Effect of OH− on morphology of Cu2O particles prepared through reduction of Cu (II) by glucose | |
| CN109437261A (en) | A kind of sheeted nanometer magnesium hydroxide raw powder's production technology | |
| CN102602946B (en) | Method for preparing white carbon black with high specific surface area by recycling wastewater containing sodium sulfate | |
| CN105060266B (en) | A kind of hydrothermal synthesis method of nano-grade lithium iron phosphate | |
| CN105731518B (en) | Normal-temperature crystallization preparation method of octahedron cuprous oxide crystal | |
| CN106865565A (en) | A kind of flyash synthesizes the method for X-type zeolite | |
| CN106430330A (en) | Preparation method of cobalt oxide powder | |
| CN108695512A (en) | The acid washing iron red purposes as negative material | |
| CN109761261B (en) | Green preparation method of cerium dioxide powder with controllable particle size and morphology and large specific surface area | |
| CN115893449B (en) | Method for producing electronic grade sodium fluoride by using industrial grade sodium-alkali mixed solution | |
| CN113772697B (en) | Nanometer lithium carbonate and preparation method thereof | |
| Li et al. | Synthesis of high purity Li2CO3 and MgCO3· 3H2O in a homogeneous-like organic phase | |
| CN106992285B (en) | A kind of preparation method of nickel cobalt aluminium ternary precursor | |
| CN104016394A (en) | Spherical nano strontium carbonate and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |