ISSN 2224-5278 (Print)
ҚАЗАҚСТАН РЕСПУБЛИКАСЫ ҰЛТТЫҚ ҒЫЛЫМ АКАДЕМИЯСЫНЫҢ
Satbayev University
Х А Б А Р Л А Р Ы
ИЗВЕСТИЯ
НАЦИОНАЛЬНОЙ АКАДЕМИИ НАУК РЕСПУБЛИКИ КАЗАХСТАН
Satbayev University
N E W S
OF THE ACADEMY OF SCIENCES OF THE REPUBLIC OF KAZAKHSTAN
Satbayev University
SERIES
OF GEOLOGY AND TECHNICAL SCIENCES
3 (441)
MAY – JUNE 2020
THE JOURNAL WAS FO67UNDED IN 1940 PUBLISHED 6 TIMES A YEAR
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Қазақстан Республикасы Ұлттық ғылым академиясы "ҚР ҰҒА Хабарлары. Геология жəне техникалық ғылымдар сериясы" ғылыми журналының Web of Science-тің жаңаланған нұсқасы Emerging Sources Citation Index-те индекстелуге қабылданғанын хабарлайды. Бұл индекстелу барысында Clarivate Analytics компаниясы журналды одан əрі the Science Citation Index Expanded, the Social Sciences Citation Index жəне the Arts & Humanities Citation Index-ке қабылдау мəселесін қарастыруда. Webof Science зерттеушілер, авторлар, баспашылар мен мекемелерге контент тереңдігі мен сапасын ұсынады. ҚР ҰҒА Хабарлары. Геология жəне техникалық ғылымдар сериясы Emerging Sources Citation Index-ке енуі біздің қоғамдастық үшін ең өзекті жəне беделді геология жəне техникалық ғылымдар бойынша контентке адалдығымызды білдіреді.
НАН РК сообщает, что научный журнал «Известия НАН РК. Серия геологии и технических наук» был принят для индексирования в Emerging Sources Citation Index, обновленной версии Web of Science. Содержание в этом индексировании находится в стадии рассмотрения компанией Clarivate Analytics для дальнейшего принятия журнала в the Science Citation Index Expanded, the Social Sciences Citation Index и the Arts & Humanities Citation Index. Web of Science предлагает качество и глубину контента для исследователей, авторов, издателей и учреждений.
Включение Известия НАН РК. Серия геологии и технических наук в Emerging Sources Citation Index демонстрирует нашу приверженность к наиболее актуальному и влиятельному контенту по геологии и техническим наукам для нашего сообщества.
Б а с р е д а к т о р ы
э. ғ. д., профессор, ҚР ҰҒА академигі И.К. Бейсембетов
Бас редакторының орынбасары Жолтаев Г.Ж. проф., геол.-мин. ғ. докторы
Р е д а к ц и я а л қ а с ы:
Абаканов Т.Д. проф. (Қазақстан)
Абишева З.С. проф., академик (Қазақстан) Агабеков В.Е. академик (Беларусь)
Алиев Т. проф., академик (Əзірбайжан) Бакиров А.Б. проф., (Қырғызстан) Беспаев Х.А. проф. (Қазақстан)
Бишимбаев В.К. проф., академик (Қазақстан) Буктуков Н.С. проф., академик (Қазақстан) Булат А.Ф. проф., академик (Украина) Ганиев И.Н. проф., академик (Тəжікстан) Грэвис Р.М. проф. (АҚШ)
Ерғалиев Г.К. проф., академик (Қазақстан) Жуков Н.М. проф. (Қазақстан)
Қожахметов С.М. проф., академик (Казахстан) Конторович А.Э. проф., академик (Ресей) Курскеев А.К. проф., академик (Қазақстан) Курчавов А.М. проф., (Ресей)
Медеу А.Р. проф., академик (Қазақстан)
Мұхамеджанов М.А. проф., корр.-мүшесі (Қазақстан) Нигматова С.А. проф. (Қазақстан)
Оздоев С.М. проф., академик (Қазақстан) Постолатий В. проф., академик (Молдова) Ракишев Б.Р. проф., академик (Қазақстан) Сейтов Н.С. проф., корр.-мүшесі (Қазақстан)
Сейтмуратова Э.Ю. проф., корр.-мүшесі (Қазақстан) Степанец В.Г. проф., (Германия)
Хамфери Дж.Д. проф. (АҚШ) Штейнер М. проф. (Германия)
«ҚР ҰҒА Хабарлары. Геология жəне техникалық ғылымдар сериясы».
ISSN 2518-170X (Online), ISSN 2224-5278 (Print)
Меншіктенуші: «Қазақстан Республикасының Ұлттық ғылым академиясы» РҚБ (Алматы қ.).
Қазақстан республикасының Мəдениет пен ақпарат министрлігінің Ақпарат жəне мұрағат комитетінде 30.04.2010 ж. берілген №10892-Ж мерзімдік басылым тіркеуіне қойылу туралы куəлік.
Мерзімділігі: жылына 6 рет.
Г л а в н ы й р е д а к т о р д. э. н., профессор, академик НАН РК
И. К. Бейсембетов Заместитель главного редактора Жолтаев Г.Ж. проф., доктор геол.-мин. наук
Р е д а к ц и о н н а я к о л л е г и я:
Абаканов Т.Д. проф. (Казахстан)
Абишева З.С. проф., академик (Казахстан) Агабеков В.Е. академик (Беларусь)
Алиев Т. проф., академик (Азербайджан) Бакиров А.Б. проф., (Кыргызстан) Беспаев Х.А. проф. (Казахстан)
Бишимбаев В.К. проф., академик (Казахстан) Буктуков Н.С. проф., академик (Казахстан) Булат А.Ф. проф., академик (Украина) Ганиев И.Н. проф., академик (Таджикистан) Грэвис Р.М. проф. (США)
Ергалиев Г.К.проф., академик (Казахстан) Жуков Н.М. проф. (Казахстан)
Кожахметов С.М. проф., академик (Казахстан) Конторович А.Э. проф., академик (Россия) Курскеев А.К. проф., академик (Казахстан) Курчавов А.М. проф., (Россия)
Медеу А.Р. проф., академик (Казахстан)
Мухамеджанов М.А. проф., чл.-корр. (Казахстан) Нигматова С.А. проф. (Казахстан)
Оздоев С.М. проф., академик (Казахстан) Постолатий В. проф., академик (Молдова) Ракишев Б.Р. проф., академик (Казахстан) Сеитов Н.С. проф., чл.-корр. (Казахстан)
Сейтмуратова Э.Ю. проф., чл.-корр. (Казахстан) Степанец В.Г. проф., (Германия)
Хамфери Дж.Д. проф. (США) Штейнер М. проф. (Германия)
«Известия НАН РК. Серия геологии и технических наук».
ISSN 2518-170X (Online), ISSN 2224-5278 (Print)
Собственник: Республиканское общественное объединение «Национальная академия наук Республики Казахстан (г. Алматы).
Свидетельство о постановке на учет периодического печатного издания в Комитете информации и архивов Министерства культуры и информации Республики Казахстан №10892-Ж, выданное 30.04.2010 г.
Периодичность: 6 раз в год.
Тираж: 300 экземпляров.
Адрес редакции: 050010, г. Алматы, ул. Шевченко, 28, ком. 219, 220, тел.: 272-13-19, 272-13-18, http://www.geolog-technical.kz/index.php/en/
Национальная академия наук Республики Казахстан, 2020 Адрес редакции: Казахстан, 050010, г. Алматы, ул. Кабанбай батыра, 69а.
Институт геологических наук им. К. И. Сатпаева, комната 334. Тел.: 291-59-38.
Адрес типографии: «NurNaz GRACE», г. Алматы, ул. Рыскулова, 103.
E d i t o r i n c h i e f
doctor of Economics, professor, academician of NAS RK I. K. Beisembetov
Deputy editor in chief
Zholtayev G.Zh. prof., dr. geol-min. sc.
E d i t o r i a l b o a r d:
Abakanov Т.D. prof. (Kazakhstan)
Abisheva Z.S. prof., academician (Kazakhstan) Agabekov V.Ye. academician (Belarus) Aliyev Т. prof., academician (Azerbaijan) Bakirov А.B. prof., (Kyrgyzstan)
Bespayev Kh.А. prof. (Kazakhstan)
Bishimbayev V.K. prof., academician (Kazakhstan) Buktukov N.S. prof., academician (Kazakhstan) Bulat А.F. prof., academician (Ukraine)
Ganiyev I.N. prof., academician (Tadjikistan) Gravis R.М. prof. (USA)
Yergaliev G.K. prof., academician (Kazakhstan) Zhukov N.М. prof. (Kazakhstan)
Kozhakhmetov S.М. prof., academician (Kazakhstan) Kontorovich А.Ye. prof., academician (Russia) Kurskeyev А.K. prof., academician (Kazakhstan) Kurchavov А.М. prof., (Russia)
Medeu А.R. prof., academician (Kazakhstan)
Muhamedzhanov M.A. prof., corr. member. (Kazakhstan) Nigmatova S.А. prof. (Kazakhstan)
Ozdoyev S.М. prof., academician (Kazakhstan) Postolatii V. prof., academician (Moldova) Rakishev B.R. prof., academician (Kazakhstan) Seitov N.S. prof., corr. member. (Kazakhstan)
Seitmuratova Ye.U. prof., corr. member. (Kazakhstan) Stepanets V.G. prof., (Germany)
Humphery G.D. prof. (USA) Steiner М. prof. (Germany)
News of the National Academy of Sciences of the Republic of Kazakhstan. Series of geology and technology sciences.
ISSN 2518-170X (Online), ISSN 2224-5278 (Print)
Owner: RPA "National Academy of Sciences of the Republic of Kazakhstan" (Almaty).
The certificate of registration of a periodic printed publication in the Committee of information and archives of the Ministry of culture and information of the Republic of Kazakhstan N 10892-Ж, issued 30.04.2010.
Periodicity: 6 times a year.
N E W S
OF THE NATIONAL ACADEMY OF SCIENCES OF THE REPUBLIC OF KAZAKHSTAN SERIES OF GEOLOGY AND TECHNICAL SCIENCES
ISSN 2224-5278
Volume 3, Number 441 (2020), 211 – 214 https://doi.org/10.32014/2020.2518-170X.77 UDC 66.669.2
IRSTI 44.41.29;53.37.35;61.31.51;53.01.91
D. S. Zhumabayeva1,G. K. Bishimbayeva1, A. K. Zhanabaeva1,2, A. M. Nalibayeva1, Y. N. Abdikalykov1
1D.V. Sokolsky Institute of Fuel, Catalysis and Electrochemistry, Almaty, Kazakhstan;
2Department of Chemical Engineering, Kazakh-British Technical University, Almaty, Kazakhstan.
E-mail: g.bishimbayeva@ifce.kz
FULL CYCLE TECHNOLOGY OF LITHIUM ELECTRODE MATERIALS FOR LIB FROM DOMESTIC RAW MATERIALS
Abstract. In recent years, there has been a steady increase in lithium consumption in high technology.
Therefore, new methods for the extraction of lithium are becoming increasingly important. The distribution of lithium stocks in the world is uneven, access to its stocks plays a significant role and affects technological development. Rare-metal pegmatites and lithium-bearing brine are used as the main industrial sources of lithium.
This paper discusses the development trends of lithium production from spodumene ore to produce high purity lithium carbonate. The geological characteristics of the main lithium deposits of East Kazakhstan, as well as the possibility of their industrial development, are analyzed. A technology has been developed to produce battery grade lithium carbonate from Kazakhstan spodumene concentrate. Based on high purity lithium carbonate (99.5%), the efficient cathode material LiFePO4 for lithium-ion batteries was synthesized. The technology of a full cycle of processing domestic lithium-containing mineral and industrial raw materials into lithium carbonate for the production of high-tech products: anode and cathode materials for modern LIB is presented. An efficient technology of lithium electrode materials based on high-purity lithium carbonate from domestic spodumene raw materials has been developed. The fundamental possibility of creating a lithium cluster in Kazakhstan for the production of
products with a high degree of readiness for the final consumer is shown according to the scheme: Sodumene ores → Lithium concentrate → Lithium carbonate → Lithium cathode materials → Batteries.
Key words: lithium, extraction, ore, spodumene, technology, lithium carbonate, lithium iron phosphate, lithium-ion battery.
Today, lithium is becoming increasingly popular in high-tech industries such as aircraft manufacturing, space industry, automotive, nuclear, energy, as well as in energy storage systems. In connection with the sharp increase in the production of electric vehicles in the world, lithium has come to be called “future gasoline” and “white oil”. Lithium-ion batteries (LIB) are the market leaders among all available battery technologies. Due to their high energy density, stability and duration of charge-discharge circulation, LIBs are the most promising sources for the needs of alternative energy. The trend towards green energy due to the exhaustibility of hydrocarbons in recent decades has given a great impetus to the development and use of lithium-ion batteries (LIBs). The rapid development of the market for battery devices, especially electric and hybrid cars and renewable energy, over the past 10 years has led to a sharp demand for higher-capacity materials for LIB. All this, as well as the development of technologies in portable electronics (phones and laptops / tablets) and electric vehicles, has led to the fact that lithium is becoming a new strategic material that can influence the sustainable development of the global economy.
The market has an urgent task to produce lithium salts, in particular lithium carbonate as the main precursor of lithium electrode materials. The main lithium minerals suitable for producing lithium concentrates, as a rule, are part of rare-metal granite pegmatites. Pegmatite mineral concentrates account for> 60% of lithium production; of these, spodumene is the main raw material for producing lithium carbonate. High purity lithium carbonate of battery quality is the main precursor of lithium electrode materials [1].
The analysis shows that the current global lithium consumption environment is favorable for the emergence of a new producer of lithium compounds, such as Kazakhstan, which has investment-attractive proven large reserves of lithium-containing ores in the Eastern region. Kazakhstan has large reserves of various rare-earth metals and their accompanying lithium. According to the degree of readiness for development and development costs, lithium deposits of the East Kazakhstan region can be divided into two groups. The first group includes mineral deposits of lithium, in which more than 23 thousand tons of lithium oxide and other useful components are concentrated. Given the forecast for the intensive development of the lithium economy, these lithium reserves are of practical interest for their development.
A promising lithium-containing technogenic object is dumps after ore beneficiation of the deposit, formed as a result of their processing at the Belogorsk mining and processing plant. Over the period of his work, more than 32 thousand tons of lithium are in the dumps of processing plants.
All this sets the task of creating a new lithium industry in Kazakhstan in order to become an important player in the world market of storage systems and energy sources, renewable energy, and electronics.
The objective of the proposed technology is the development of a method for obtaining high-grade lithium carbonate directly from spodumene, by passing the stage of obtaining a technical grade product, simplifying the process of cleaning a lithium-containing solution from impurities.
The technical result is to obtain high-grade lithium carbonate in a single technological process of processing spodumene, reducing the number of technological operations of cleaning from impurities, eliminating the expensive operation of concentrating a solution of lithium sulfate by the method of evaporation [2].
The technical result is achieved by a method of obtaining high-grade lithium carbonate from spodumene concentrate, including spodumen calcining, sulfation, water leaching, purification of lithium sulfate from impurities, lithium concentration in solution, reagent lithium carbonate precipitation, washing of lithium carbonate, characterized in that lithium concentration is carried out by a membrane method reverse osmosis, cleaning of metal and anions from impurities is carried out by causification of lithium sulfate, lithium carbonate is deposited by ammonium carbonate salt at a temperature not more than 40 оC, followed by heating to 90 оC. An essential feature of the method is the use of reverse osmosis membranes for the concentration of a solution of lithium sulfate, which makes it possible to exclude from the technology a very laborious and expensive method of evaporation of a solution of lithium sulfate [3].
Further purification, including caustification of lithium carbonate, ultrafiltration and ion-exchange sorption of a lithium hydroxide solution followed by precipitation with ammonium carbonate salt, bicarbonization and decarbonization of lithium carbonate, made it possible to obtain high purity lithium carbonate 99.5% [4].
Innovative electrode materials for LIB were obtained from high purity lithium carbonate on the basis of domestic spodumene raw materials by synthesis using method of aerosol pyrolysis (MAP) and sol-gel method (ZGM). Thus obtained lithium- iron- phosphate showed quite satisfactory electrochemical properties [5].
The end result is a new generation of innovative cathode and anode materials for modern LIBs with significantly increased capacity and stability, obtained from lithium precursors - battery grade lithium carbonate based on domestic spodumene raw materials.
Thus, technologies have been developed for producing innovative electrode materials for modern lithium batteries with the creation of a full cycle of the production line from lithium extraction from domestic mineral raw materials to high-tech products - cathode and anode materials of modern lithium-ion
Д. С. Жумабаева1, Г. К. Бишимбаева1, А. К. Жанабаева1,2, А. М. Налибаева1, Е. Н. Абдикалыков1
1«Д. В. Сокольский атындағы жанармай, катализ жəне электрохимия институты» АҚ, Алматы, Қазақстан;
2«Химиялық инженерия» ғылыми білім беру орталығы, Қазақстан-Британ техникалық университеті, Алматы, Қазақстан
ОТАНДЫҚ ШИКІЗАТТАН АЛЫНҒАН ЛИБ-КЕ АРНАЛҒАН ЛИТИЙЛІ ЭЛЕКТРОДТЫ МАТЕРИАЛДАР ТЕХНОЛОГИЯСЫНЫҢ ТОЛЫҚ ЦИКЛІ
Аннотация. Соңғы жылдары жоғары технологияда литийді тұтынудың тұрақты өсу қарқыны байқалады. Сондықтан литий алудың жаңа əдістері барған сайын маңызды бола түсуде. Əлемде литий қорларының таралуы біркелкі емес, оның қорларына қол жеткізу маңызды болып саналады жəне технологиялық дамуға əсер етеді.
Бұл жұмыста жоғары таза литий карбонатын алу үшін сподумен кендерінен литийді өндірудің даму тенденциялары қарастырылды. Шығыс Қазақстанның негізгі литий кен орындарының геологиялық сипаттамалары, сондай-ақ олардың өнеркəсіптік даму мүмкіндігі талданды. Қазақстандық сподумен концентратынан батарея сапасындағы литий карбонатын алу технологиясы əзірленді. Жоғары таза литий карбонатынан (99,5%) литий-ионды аккумуляторлар үшін тиімді LiFePO4 катодты материалы синтезделді.
Жоғары технологиялық өнім: заманауи литий-ионды батареяларға (ЛИБ) арналған анод жəне катод материалдарын алу үшін отандық литий құрамды минералды жəне техногенді шикізатты литий карбонатына өңдеудің технологиясының толық циклі ұсынылды. Отандық сподумен шикізатынан литий карбонат негізіндегі литий электродты материалдарын алудың тиімді технологиясы əзірленді. Соңғы тұтынушыға жоғары дəрежедегі дайын өнім шығаруға арналған Қазақстанда литий кластерін құрудың негізгі мүмкіндігі келесі схемаға сəйкес көрсетілген: Сподуменді кендер → Литийді концентрат → литий карбонаты → Литийді катодтық материалдар → Аккумуляторлар.
Түйін сөздер: литий, экстракция, кен, сподумен, технология, литий карбонаты, литий темір фосфаты, литий-ионды аккумулятор.
Д. С. Жумабаева1, Г. К. Бишимбаева1, А. К. Жанабаева1,2, А. М. Налибаева1, Е. Н. Абдикалыков1
1Институт топлива, катализа и электрохимии им. Д. В. Сокольского, Алматы, Казахстан;
2Научно–образовательный центр «Химическая инженерия», Казахстанско-Британский технический университет, Алматы, Казахстан
ТЕХНОЛОГИЯ ПОЛНОГО ЦИКЛА ЛИТИЕВЫХ ЭЛЕКТРОДНЫХ МАТЕРИАЛОВ ДЛЯ ЛИБ ИЗ ОТЕЧЕСТВЕННОГО СЫРЬЯ
Аннотация. В последние годы наблюдается устойчивый рост потребления лития в области высоких технологий. Поэтому все большее значение имеют новые методы извлечения лития. Распределение запасов лития в мире неравномерно, доступ к его запасам играет значительную роль и влияет на технологическое развитие. В качестве основных промышленных источников лития используют редкометальные пегматиты и литиеносную рапу.
В настоящей работе рассмотрены тенденции развития производства лития из сподуменовой руды для получения карбоната лития высокой чистоты. Проанализированы геологические характеристики основных литиевых месторождений Восточного Казахстана, а также возможности их промышленного освоения.
Разработана технология получения карбоната лития аккумуляторного сорта из казахстанского сподуменового концентрата. На основе карбоната лития высокой чистоты (99,5%) синтезирован эффективный катодный материал LiFePO4 для литий-ионных батарей (ЛИБ). Представлена технология полного цикла переработки отечественного литийсодержащего минерального и техногенного сырья в карбонат лития для производства высокотехнологичной продукции: анодных и катодных материалов для современных ЛИБ. Разработана эффективная технология литиевых электродных материалов на основе высокочистого карбоната лития из отечественного сподуменового сырья. Показана принципиальная
возможность создания в Казахстане литиевого кластера для производства продуктов с высокой степенью готовности для конечного потребителя по схеме: сподуменовые руды → литиевый концентрат → литиевый карбонат → литиевые катодные материалы → аккумуляторы.
Ключевые слова: литий, извлечение, руда, сподумен, технология, карбонат лития, литий-железо- фосфат, литий-ионный аккумулятор.
Information about the authors:
Zhumabayeva Dinara Sarsenovna, Doctor of Engineering, PhD, Senior Researcher, D.V. Sokolsky Institute of Fuel, Catalysis and Electrochemistry, Almaty, Kazakhstan; d.zhumabayeva@ifce.kz; https://orcid.org/0000-0002- 6843-1056
Bishimbayeva Gaukhar Kozykeevna, Doctor of Technical Sciences, Professor, Chief Scientific Researcher, D.V. Sokolsky Institute of Fuel, Catalysis and Electrochemistry, Almaty, Kazakhstan; g.bishimbayeva@ifce.kz;
https://orcid.org/0000-0002-8243-1124
Zhanabaeva Asem Kaldybekkyzy, PhD student of Kazakh-British Technical University, Engineer, D.V. Sokol’skii Institute of Fuel, Catalysis and Electrochemistry, Almaty, Kazakhstan; a.k.zhanabaeva@mail.ru;
https://orcid.org/0000-0002-4738-9012
Nalibayeva Arailym Muratovna, Scientific Researcher, D.V. Sokolsky Institute of Fuel, Catalysis and Electrochemistry, Almaty, Kazakhstan; aray77@mail.ru; https://orcid.org/0000-0003-3976-5134
Abdikalykov Yerlan Nurzhanuly, Undergraduate of al-Farabi Kazakh National University, Engineer, D.V. Sokol’skii Institute of Fuel, Catalysis and Electrochemistry, Almaty, Kazakhstan;
abdikalykov.yerlan@gmail.com; https://orcid.org/0000-0003-0502-942X REFERENCES
[1] Martin G., Rentsch L., Hoeck M., Bertau M. (2017) Lithium market research - global supply, future demand and price development, Energy Storage Mater. 6: 171-179.
[2] Bishimbayeva G., Zhumabayeva D., Zhandayev N., Nalibayeva A., Shestakov K., Levanevsky I., Zhanabayeva A.
(2018) Technological improvement lithium recovery methods from primary resources, Oriental Journal of Chemistry. 34.
6: 2762-2769. DOI: 10.13005/ojc/340611
[3] Levanevskij I.O, Stolbova E.F., Shestakov K.A., Shulgin K.L., Zhandayev N.M., Bishimbayeva G.K., Zhumabayeva D.S. (2019) Method of obtaining high-grade lithium carbonate from spodumene concentrate [Sposob polucheniya vysokosortnogo karbonata litiya iz spodumenovogo koncentrata] (in Russ.).
[4] Bishimbayeva G.K., Zhumabayeva D.S., NalibayevaA.M., ZhanabayevaA.K. (2020) The method of producing high purity lithium carbonate [Sposob polucheniya vysokochistogo karbonata litiya] (in Russ.).
[5] Bishimbayeva G.K., Zhumabayeva D.S., Zhandayev N.M, Bakenov Z.B, Nalibayeva A.M. (2018) Spray Pirolysis Synthesis of Electrode Materials from the Domestic Lithium Carbonate. XXVIII International Conference on Organometallic Chemistry, Florence, Italy. 548 p.
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