二氧化硅基气凝胶材料及其制备技术的专利分析

doi:10.16085/j.issn.1000-6613.2023-0673

摘要/Abstract

摘要：

气凝胶为多功能新型材料，其中二氧化硅基气凝胶是研究最广泛的气凝胶材料，2004年首次在中国产业化，至今被广泛应用于电子、建筑、隔热、航空航天、能源等领域中。但与国外相比，中国高端产品较少，原始创新略显不足。因此，本文梳理了近20年全球二氧化硅基气凝胶材料及其制备技术的相关专利，从专利的视角挖掘近20年的研究热点。从市场流向和重点申请人的维度分析当前的市场竞争格局，指出以美、德、日为代表的发达国家，通过全球专利布局在一定程度上实现了对市场较大力度的控制，处于领先地位。重点从技术热点及技术路线的角度分析二氧化硅基气凝胶及其制备技术的研究热点：目前，气凝胶颗粒、前体的改进和纤维增强是近年来该领域的研究重点，各国对金属氧化物复合材料和透明储能材料的关注度较高。并且通过梳理中国的转移转化专利的技术特点，帮助企业在寻求技术合作时精准找到合作对象。最后总结了技术创新中中国企业需重点关注的研究方向，为未来的技术研发提供指引。

关键词: 二氧化硅基, 气凝胶, 金属氧化物复合材料, 专利分析

Abstract:

Aerogel is a multifunctional new material. The silica-based aerogel as the most widely studied aerogel material, first industrialized in China in 2004, has been widely used in electronics, construction, thermal insulation, aerospace, energy and other fields. However, compared with foreign countries, there are fewer high-end products in China and the original innovation is slightly insufficient. In this paper, the patents related to silica-based aerogel materials and its preparation technology in the past 20 years were studied and the research hotspots in the past 20 years from the perspective of patents were explored. This paper analyzed the current market competition pattern from the dimensions of market flow and key applicants, and pointed out that the developed countries represented by the United States, Germany and Japan were in the leading position through the global patent layout to achieve a greater control of the market to a certain extent. It focused on analyzing the research hotspots of silica-based aerogel and its preparation technology from the perspectives of technical hotspots and technical routes. At present, aerogel particles, precursor improvement and fiber reinforcement were the research focuses in this field in recent years, and all countries had paid more attention to metal oxide composites and transparent energy storage materials. Then, by sorting out the technical characteristics of Chinese transferred and transformed patents, it helped enterprises to accurately find cooperation partners when seeking technical cooperation. Finally, the research directions that Chinese enterprises needed to focus on in technological innovation were summarized to provide guidelines for future technological research and development.

Key words: silica-based, aerogel, metal oxide composites, patent analysis

中图分类号:

TB332

熊文婷, 罗启基, 鄢春根. 二氧化硅基气凝胶材料及其制备技术的专利分析[J]. 化工进展, 2024, 43(4): 1912-1922.

XIONG Wenting, LUO Qiji, YAN Chungen. Silica-based aerogel materials and their preparation technology from a patent analysis[J]. Chemical Industry and Engineering Progress, 2024, 43(4): 1912-1922.

图/表 9

参考文献 31

1	米歇尔·安德烈·埃杰尔特, 尼古拉斯·莱文蒂斯, 马蒂亚斯·M·科贝尔. 气凝胶手册[M]. 任洪波, 崔旭东, 译. 北京: 中国原子能出版社, 2014: 4-11.
	MICHEL Andre Egert, NICOLAS Levintis, Kobel MADIAS M. Aerogels handbook[M]. REN Hongbo, CUI Xudong, trans. Beijing: China Atomic Energy Press, 2014: 4-11.
2	KISTLER S S. Coherent expanded aerogels and jellies[J]. Nature, 1931, 127(3211): 741.
3	贾艳萍, 马姣, 张兰河, 等. 多孔二氧化硅材料的应用进展[J]. 硅酸盐通报, 2014, 33(12): 3206-3212.
	JIA Yanping, MA Jiao, ZHANG Lanhe, et al. Application progress on porous silica material[J]. Bulletin of the Chinese Ceramic Society, 2014, 33(12): 3206-3212.
4	梁玉莹, 吴会军, 游秀华, 等. 纤维改善SiO₂气凝胶的力学和隔热性能研究进展[J]. 硅酸盐通报, 2017, 36(4): 1216-1222.
	LIANG Yuying, WU Huijun, YOU Xiuhua, et al. Advances in effect of fiber species on improving mechanical and thermal insulation properties of silica aerogel[J]. Bulletin of the Chinese Ceramic Society, 2017, 36(4): 1216-1222.
5	任富建, 杨万吉, 张蕊, 等. 疏水二氧化硅气凝胶的常压制备及性能研究[J]. 无机盐工业, 2015, 47(10): 38-40.
	REN Fujian, YANG Wanji, ZHANG Rui, et al. Synthesis and characterization of hydrophobic silica aerogels via ambient pressure drying[J]. Inorganic Chemicals Industry, 2015, 47(10): 38-40.
6	罗燚, 姜勇刚, 冯军宗, 等. 常压干燥制备SiO₂气凝胶复合材料研究进展[J]. 材料导报, 2018, 32(5): 780-787.
	LUO Yi, JIANG Yonggang, FENG Junzong, et al. Progress on the preparation of SiO₂ aerogel composites by ambient pressure drying technique[J]. Materials Review, 2018, 32(5): 780-787.
7	TABATA Makoto, ADACHI Ichiro, KAWAI Hideyuki, et al. Recent progress in silica aerogel Cherenkov radiator[J]. Physics Procedia, 2012, 37: 642-649.
8	JUNG In-Keun, GURAV Jyoti L, Tae-Jung HA, et al. The properties of silica aerogels hybridized with SiO₂ nanoparticles by ambient pressure drying[J]. Ceramics International, 2012, 38: S105-S108.
9	SCHIMIZZE Benjamin, Steven F SON, GOEL Rahul, et al. An experimental and numerical study of blast induced shock wave mitigation in sandwich structures[J]. Applied Acoustics, 2013, 74(1): 1-9.
10	CUCE Erdem, CUCE Pinar Mert, WOOD Christopher J, et al. Toward aerogel based thermal superinsulation in buildings: A comprehensive review[J]. Renewable and Sustainable Energy Reviews, 2014, 34: 273-299.
11	舒心, 刘朝辉, 丁逸栋, 等. 纳米SiO₂气凝胶的制备及保温隔热性应用研究进展[J]. 材料导报, 2018, 32(5): 788-795.
	SHU Xin, LIU Zhaohui, DING Yidong, et al. Preparation and application of nano-silica aerogels in thermal insulation: An overview[J]. Materials Review, 2018, 32(5): 788-795.
12	潘月磊, 程旭东, 闫明远, 等. 二氧化硅气凝胶及其在保温隔热领域应用进展[J]. 化工进展, 2023, 42(1): 297-309.
	PAN Yuelei, CHENG Xudong, YAN Mingyuan, et al. Silica aerogel and its application in the field of thermal insulation[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 297-309.
13	国家知识产权局知识产权运用促进司. GB/T 39551《专利导航指南》系列标准解读[M]. 北京: 中国标准出版社, 2022: 141.
	Intellectual Property Application Promotion Department of China National Intellectual Property Administration. Interpretation of GB/T 39551 patent navigation guide series standards[M]. Beijing: Standards Press of China, 2022: 141.
14	中华人民共和国国家知识产权局. 专利审查指南-2010[M]. 修订版. 北京: 知识产权出版社, 2017: 93.
	China National Intellectual Property Administration. Guide to patent examination-2010[M]. Revised ed. Beijing: Intellectual Property Press, 2017: 93.
15	乌尔里克·鲍尔, 迈克尔·S·达西罗, 雷克斯·J·菲尔德, 等. 气凝胶颗粒及其制造方法: CN101679657A[P]. 2010-03-24.
	ULRICH BAUER, DARSILLO MICHAEL S, FIELD REX J, et al. Aerogel particles and methods of making same: CN101679657A[P]. 2010-03-24.
16	CHEN Jeanhong, CHEN Shiushiu, PONG Shenghong. Method for producing a heat insulating material composed of a hydrophobic aerogel and the application thereof: US20210332586A1[P]. 2021-10-28.
17	GRASER Fritz, STANGE Andereas. Process for obtaining aerogels: EP0171722A3[P]. 1986-02-19.
18	马利国, 孙艳荣, 李东来, 等. 二氧化硅气凝胶硅源选择的研究进展[J]. 无机盐工业, 2020, 52(8): 11-16.
	MA Liguo, SUN Yanrong, LI Donglai, et al. Research progress on silicon source selection of silica aerogel[J]. Inorganic Chemicals Industry, 2020, 52(8): 11-16.
19	李晓雷, 何健, 胡志鹏, 等. 超弹性SiO₂气凝胶的制备及其吸附有机溶剂和重金属性能研究[C]//中国硅酸盐学会,国际玻璃协会TC-16. 2016中国溶胶-凝胶学术研讨会暨国际论坛论文摘要集. 湖南:2016中国溶胶-凝胶学术研讨会暨国际论坛, 2016: 59.
	LI Xiaolei, HE Jian, HU Zhipeng, et al. Preparation of super-elastic SiO₂ aerogels for effective absorption of oil and heavy metal ion[C]//The Chinese Ceramic Society, International Commission on Glass TC-16. 2016 Sol-Gel Symposium of China & International Forum. Hunan: 2016 Sol-Gel Symposium of China & International Forum, 2016: 59.
20	李治. 增韧疏水性二氧化硅气凝胶制备及燃烧性能研究[D]. 合肥: 中国科学技术大学, 2017.
	LI Zhi. Preparation and combustion performance of toughen hydrophobic silica aerogels[D].Hefei: University of Science and Technology of China, 2017.
21	TIAN Yu, FENG Juanjuan, WANG Xiuqin, et al. An organic-inorganic hybrid silica aerogel prepared by co-precursor method for solid-phase microextraction coating[J]. Talanta, 2019, 194: 370-376.
22	罗丹, 龙丽娟, 秦舒浩, 等. 玻璃纤维和碳纤维增强二氧化硅气凝胶复合材料的制备及性能研究[J]. 化工新型材料, 2022, 50(4): 161-165.
	LUO Dan, LONG Lijuan, QIN Shuhao, et al. Preparation and property of GF and CF reinforced SiO₂ aerogel composites[J]. New Chemical Materials, 2022, 50(4): 161-165.
23	王杰, 施玲艳, 苏琮轩, 等. 二氧化硅气凝胶用纤维研究进展[J]. 现代化工, 2023, 43(5): 45-49.
	WANG Jie, SHI Lingyan, SU Congxuan, et al. Research progress on fibers used for silica aerogel[J]. Modern Chemical Industry, 2023, 43(5): 45-49.
24	吕伯昇, 秦磊, 茹瑞, 等. 新型纳米颗粒/SiO₂复合气凝胶制备及吸附催化应用进展[J]. 化工进展, 2020, 39(12): 5095-5103.
	Bosheng LYU, QIN Lei, RU Rui, et al. Progress on the preparation of nanomaterials-SiO₂ aerogel composites and their applications in adsorption and catalysis[J]. Chemical Industry and Engineering Progress, 2020, 39(12): 5095-5103.
25	张学同, 杜煜. 一种超透明氧化硅气凝胶材料、其制备方法及应用: CN115057447A[P]. 2022-09-16.
	ZHANG Xuetong, DU Yu. Super-transparent silicon oxide aerogel material as well as preparation method and application thereof: CN115057447A[P]. 2022-09-16.
26	张晚林, 李文静, 刘圆圆, 等. 一种透明度可调的超低密度二氧化硅气凝胶及其制备方法和应用: CN113247912B[P]. 2021-11-02.
	ZHANG Wanlin, LI Wenjing, LIU Yuanyuan, et al. Ultralow-density silicon dioxide aerogel with adjustable transparency, and preparation method and application thereof: CN113247912B[P]. 2021-11-02.
27	赵耀耀, 杨志国, 郭卫疆, 等. 一种透明氧化硅气凝胶块体材料的制备方法: CN113582187A[P]. 2021-11-02.
	ZHAO Yaoyao, YANG Zhiguo, GUO Weijiang, et al. Preparation method of transparent silicon oxide aerogel block material: CN113582187A[P]. 2021-11-02.
28	卢斌, 卢孟磊, 张丁日, 等. 一种增强型透明二氧化硅气凝胶及其制备方法: CN109179428B[P]. 2020-10-02.
	LU Bin, LU Menglei, ZHANG Dingri, et al. Enhanced type transparent silicon dioxide aerogel and preparation method thereof: CN109179428B[P]. 2020-10-02.
29	张晚林, 刘圆圆, 李文静, 等. 一种可后清洁的超低密度透明二氧化硅气凝胶及其制备方法和应用: CN112299428B[P]. 2022-02-15.
	ZHANG Wanlin, LIU Yuanyuan, LI Wenjing, et al. Ultralow-density transparent silicon dioxide aerogel capable of being post-cleaned as well as preparation method and application of ultralow-density transparent silicon dioxide aerogel: CN112299428B[P]. 2022-02-15.
30	国泰君安证券. 晨光新材研究报告: 功能性硅烷再出发, 潜在气凝胶优势领先[R/OL]. (2022-04-23) [2023-04-20]..
	Guotai Junan Securities. Research report of Chenguang New Material: Functional silanes revisited, potential aerogel advantages lead the way[R/OL]. (2022-04-23) [2023-04-20]. .
31	国家知识产权局战略规划司. 2022中国专利调查报告[R/OL]. (2022-02-18) [2023-04-20]. .
	Strategic Planning Department of China National Intellectual Property Administration. 2022 China Patent Investigation Report[R/OL]. (2022-02-18) [2023-04-20]. .

IPC	释义
C01B33/158	提纯；干燥；脱水的硅；其化合物（C01B21/00， C01B 23/00优先；过硅酸盐入C01B15/14；碳化物入C01B32/956）[2006.01]
B01J13/00	胶体化学，例如，其他类目中不包括的胶体物料或其溶液的制备；微胶囊或微球的制造[2006.01]
C01B33/14	胶体硅石，如分散体、凝胶、溶胶的硅；其化合物（C01B21/00，C01B23/00优先；过硅酸盐入C01B15/14；碳化物入C01B32/956）[2006.01]
C01B33/00	硅；其化合物（C01B21/00，C01B23/00优先；过硅酸盐入C01B15/14；碳化物入C01B32/956）[2006.01]
C01B33/141	水溶胶或水分散体的制备，如分散体、凝胶、溶胶的硅；其化合物（C01B21/00，C01B23/00优先；过硅酸盐入C01B15/14；碳化物入C01B32/956）[2006.01]
C01B33/12	硅石；其水合物，如勒皮硅酸；其化合物（C01B21/00，C01B23/00优先；过硅酸盐入C01B15/14；碳化物入C01B32/956）[2006.01]
C01B33/16	硅干凝胶的制备；其化合物（C01B21/00，C01B23/00优先；过硅酸盐入C01B15/14；碳化物入C01B32/956）[2006.01]
C04B30/02	含有纤维状材料的不含黏结剂的人造石组合物（用熔渣制造的人造石入C04B5/00）[2006.01]

IPC	释义
C01B33/158	提纯；干燥；脱水的硅；其化合物（C01B21/00， C01B 23/00优先；过硅酸盐入C01B15/14；碳化物入C01B32/956）[2006.01]
B01J13/00	胶体化学，例如，其他类目中不包括的胶体物料或其溶液的制备；微胶囊或微球的制造[2006.01]
C01B33/14	胶体硅石，如分散体、凝胶、溶胶的硅；其化合物（C01B21/00，C01B23/00优先；过硅酸盐入C01B15/14；碳化物入C01B32/956）[2006.01]
C01B33/00	硅；其化合物（C01B21/00，C01B23/00优先；过硅酸盐入C01B15/14；碳化物入C01B32/956）[2006.01]
C01B33/141	水溶胶或水分散体的制备，如分散体、凝胶、溶胶的硅；其化合物（C01B21/00，C01B23/00优先；过硅酸盐入C01B15/14；碳化物入C01B32/956）[2006.01]
C01B33/12	硅石；其水合物，如勒皮硅酸；其化合物（C01B21/00，C01B23/00优先；过硅酸盐入C01B15/14；碳化物入C01B32/956）[2006.01]
C01B33/16	硅干凝胶的制备；其化合物（C01B21/00，C01B23/00优先；过硅酸盐入C01B15/14；碳化物入C01B32/956）[2006.01]
C04B30/02	含有纤维状材料的不含黏结剂的人造石组合物（用熔渣制造的人造石入C04B5/00）[2006.01]

项目	中国	美国	日本	德国	韩国
隔热绝缘材料	●	●	●	●	●
纤维增强	●	●	●	●	●
表面/前体改性	●	●	●	●	●
石墨烯复合材料	●	●	●	●	●
透明储能材料	●	●	●	●	●
金属氧化物复合材料	●	●	●	●	●

项目	中国	美国	日本	德国	韩国
隔热绝缘材料	●	●	●	●	●
纤维增强	●	●	●	●	●
表面/前体改性	●	●	●	●	●
石墨烯复合材料	●	●	●	●	●
透明储能材料	●	●	●	●	●
金属氧化物复合材料	●	●	●	●	●

排名	申请人	国家	专利申请量/件	在华申请量/件	平均首权字数	同族国家/地区
1	乐金集团	韩国	217	176	194.10	KR/CN/EP/WO/US/JP/BR/IN
2	Aspen	美国	200	152	112.1	KR/CN/JP/EP/WO/US/IL/RU/PT/IN/DK/MX/FR/MY/HU/ES/BR/AU/SG/SI/PL/CA/TR
3	赢创工业	德国	124	106	191.58	JP/US/DE/CN/WO/EP/NO/IL/RU/PT/IN/DK/KR/ZA/MX/ES/BR/AT/AU/SI/CA/HR/IT/PL/SG
4	Cabot	美国	113	99	131	DE/JP/WO/US/EP/CN/DK/KR/MX/ES/AT/CA/AU/RU/BR/NO
5	BASF	德国	59	46	180	US/CN/JP/WO/EP/BR/AU/IN/KR/DK/MX/CA/PL
6	日立公司	日本	57	44	150.45	JP/CN/KR/WO/US/EP/CN/MY/SG
7	瓦克化学	德国	57	55	135.25	DE/JP/CN/WO/EP/US/AT/PT/DK/KR/CA/ES
8	松下集团	日本	45	29	125.69	JP/KR/WO/CN/EP/US/DE
9	航天特种材料及工艺技术研究所	中国	44	44	406.41	CN
10	南京工业大学	中国	43	43	454.7	WO/CN
11	中国科学院研究所	中国	38	38	356.32	CN
12	弗劳恩霍	德国	26	19	105.23	DE/US/CN/JP/WO/EP/IL/RU/KR/BR/AU/SG/PE/CA/ES/AT
13	EMPA	瑞士	25	14	429.81	BR/AU/IN/JP/KR/WO/EP/US/CN
14	同济大学	中国	23	23	399.48	CN
15	德山公司	日本	22	11	141.7	JP/KR/WO/CN/EP/US
16	Keey Aerogel	法国	20	19	184.56	RS/PT/JP/KR/DK/LT/CN/EP/MX/FR/HU/ES/BR/SI/WO/PL/US
17	博世公司	德国	19	13	241.25	DE/US/JP/CN/KR/WO/EP/UA/ES/BR/RU
18	罗克伍尔	丹麦	18	17	213.35	RU/CH/IN/KR/WO/CN/EP/CA/US/BR/PL/HU
19	浙江工业大学	中国	17	17	326.76	CN
20	纳诺科技	中国	15	15	348.87	CN
21	巩义市泛锐熠辉复合材料有限公司	中国	15	15	325.07	CN