SELECT CASE
         WHEN start_time <= current_time and end_time >= current_time
         THEN current_time
         ELSE NULL :: time
       END 
  FROM your_table

将求反运算符NOT与BETWEEN一起使用。

select '10:00:01'::time not between '16:00:12'::time and '22:00:00'::time;
 ?column? 
----------
 t

 select '10:00:01'::time not between '07:00:12'::time and '22:00:00'::time;
 ?column? 
----------
 f

要从表中进行选择，您需要类似以下的内容：

select time_col from the_table where time_col not between '16:00:12'::time and '22:00:00'::time;

--or

select time_col from the_table where time_col not between '07:00:12' and '22:00:00'::time;

关于SQLAlchemy，请参见介于：
从sqlalchemy导入介于
stmt =选择（用户表）.where（介于（用户表. c.标识，5，7）之间）
我相信否定它的方式应该是：
select(users_table).where(~between(users_table.c.id, 5, 7))